Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and alpha-olefin/conjugated diene copolymers

ABSTRACT

The invention provides olefin polymerization catalyst exhibiting excellent polymerization activities, a process for olefin polymerization using the catalyst, a novel transition metal compound useful for the catalyst, and an α-olefin/conjugated diene copolymer having specific properties. The olefin polymerization catalyst of the invention comprises (A) a transition metal compound of formula (I) or (II), and (B) an organometallic compound, an oranoaluminum oxy-compound or an ionizing ionic compound. The novel transition metal compound of the invention is a compound of formula (I) wherein M is a transition meal atom of Group 3 or 4 of the periodic table; m is an integer of 1 to 3; R 1  is a hydrocarbon group, etc.; R 2  to R 5  are each H, a halogen, a hydrocarbon group, etc.; R 6  is a halogen, a hydrocarbon group, etc.; n is a number satisfying a valence of M; and X is a halogen, a hydrocarbon group, etc.

FIELD OF THE INVENTION

[0001] The present invention relates to novel olefin polymerizationcatalysts, transition metal compounds and processes for olefinpolymerization using the olefin polymerization catalysts.

[0002] The present invention also relates to α-olefin /conjugated dienecopolymers which have narrow molecular weight distribution and arefavorably used as rubbers.

BACKGROUND OF THE INVENTION

[0003] As olefin polymerization catalysts, “Kaminsky catalysts” are wellknown. The Kaminsky catalysts have extremely high polymerizationactivities, and by the use of them, polymers of narrow molecular weightdistribution can be obtained. Transition metal compounds which are knownas those employable for the Kaminsky catalysts are, for example,bis(cyclopentadienyl)zirconium dichloride (see: Japanese PatentLaid-Open Publication No. 19309/1083) andethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride (see:Japanese Patent Laid-Open Publication No. 130314/1086). It is also knownthat the olefin polymerization activities or the properties of theresulting polyolefins greatly vary when different transition metalcompounds are used in the polymerization. Further, transition metalcompounds having a ligand of diimine structure have been recentlyproposed as novel olefin polymerization catalysts (see: InternationalPatent Publication No. 9623010).

[0004] By the way, polyolefins generally have excellent mechanicalproperties, and therefore they are used in many fields such as fields ofvarious molded products. However, with variation of requirements for thepolyolefins, polyolefins of various properties have been desired inrecent years. Moreover, increase of productivity has been also desired.

[0005] Under such circumstances as mentioned above, there has beendesired development of olefin polymerization catalysts having excellentolefin polymerization activities and capable of producing polyolefins ofexcellent properties.

[0006] It is well known that copolymerization of several kinds of(α-olefins and non-conjugated dienes proceeds when Ziegler-Nattapolymerization catalysts are used. Since the copolymers thus obtainedare useful as rubbers, copolymers of various types have been produced.However, the non-conjugated dienes used in the copolymerization aregenerally expensive and have low reactivity. Therefore, diene componentswhich are inexpensive and have high reactivity are desired.

[0007] Examples of such diene components include conjugated dienes suchas 1,3-butadiene and isoprene. Though these conjugated dienes are moreinexpensive and have higher reactivity as compared with the conventionalnon-conjugated dienes, they have problem such that the activities aremarkedly lowered or only ununiform copolymers of wide compositiondistribution or wide molecular weight distribution are obtained if thecopolymerization is conducted by the use of the conventionalZiegler-Natta polymerization catalysts. In case of a Ziegler-Nattacatalyst system using a vanadium compound, the polymerization activitiesare extremely low, though relatively uniform copolymers are obtainable.In the circumstances, copolymerization of ethylene and butadiene usingmetallocene catalysts which have been studied extensively and thus knownto exhibit high polymerization activities has been investigated(National Publication of International Patent No. 501633/1989).

[0008] In the above case, however, it has been reported that from thediene unit and ethylene incorporated into the polyme form togethercyclopentane skeleton in the polymer chain, and that the proportion ofthe cyclopentane skeleton becomes not less than 50% of all the dieneunits. The conversion of double bonds of the diene unit into thecyclopentane skeleton is very disadvantageous in the procedure of“vulcanization” required to use the copolymers as rubbers. Further, thecyclopentane skeleton is an unfavorable skeleton because it functions toincrease glass transition temperature of the copolymers and isdetrimental to the low-temperature properties of the rubbers.

[0009] Under these circumstances, as mentioned above, there has beeneagerly desired development of copolymers of a α-olefins and conjugateddienes, which have narrow molecular weight distribution and uniformcomposition and contain almost no cyclopentane skeleton in their polymerchains.

OBJECT OF THE INVENTION

[0010] It is an object of the present invention to provide an olefinpolymerization catalyst having excellent olefin polymerizationactivities.

[0011] It is another object of the invention to provide a noveltransition metal compound useful for such catalyst.

[0012] It is a further object of the invention to provide a process forolefin polymerization using the catalyst.

[0013] It is a still further object of the invention to provide anα-olefin/conjugated diene copolymer having a narrow molecular weightdistribution and containing almost no cyclopentane skeleton in itspolymer chain.

SUMMARY OF THE INVENTION

[0014] The first olefin polymerization catalyst according to the presentinvention comprises:

[0015] (A) a transition metal compound represented by the followingformula (I), and

[0016] (B) at least one compound selected from:

[0017] (B-1) an organometallic compound,

[0018] (B-2) an organoaluminum oxy-compound, and

[0019] (B-3) a compound which reacts with the transition metal compound(A) to form an ion pair:

[0020] wherein M is a transition metal atom of Group 3 to Group 11 ofthe periodic table,

[0021] m is an integer of 1 to 6,

[0022] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring,

[0023] when m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other,

[0024] n is a number satisfying a valence of M, and

[0025] X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring.

[0026] In the present invention, R⁶ in the formula (I) is preferably ahalogen atom, a hydrocarbon group, a heterocyclic compound residue, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group.

[0027] In the present invention, the transition metal compoundrepresented by the formula (I) is preferably a transition metal compoundrepresented by the following formula (I-a):

[0028] wherein M is a transition metal atom of Group 3 to Group 11 ofthe periodic table,

[0029] m is an integer of 1 to 3,

[0030] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylhiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group, a carboxyl group, a sulfo group, a mercapto groupor a hydroxyl group, and two or more of them may be bonded to each otherto form a ring,

[0031] when m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other,

[0032] n is a number satisfying a valence of M, and

[0033] X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring.

[0034] In the above formula (I-a), R⁶ is preferably a halogen atom, ahydrocarbon group, a heterocyclic compound residue, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, a arylthiogroup, an acyl group, an ester group, a thioester group, an amido group,an imido group, an amino group, an imino group, a sulfonester group, asulfonamido group, a cyano group, a nitro group, a carboxyl group, asulfo group, a mercapto group or a hydroxyl group

[0035] Further, the transition metal compound represented by the formula(I) is preferably a transition metal compound represented by thefollowing formula (I-a-1):

[0036] wherein M is a transition metal atom of Group 3 to Group 11 ofthe periodic table,

[0037] m is an integer of 1 to 3,

[0038] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group, and two or more of them may bebonded to each other to form a ring,

[0039] when m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other,

[0040] n is a member satisfying a valence of M, and

[0041] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group or asilicon-containing group, and when n is 2 or greater, plural groups Xmay be the same or different and may be bonded to each other to form aring.

[0042] In the formula (I-a-1), R⁶ is preferably a halogen atom, ahydrocarbon group, a heterocyclic compound residue, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, an acyl group, an ester group, a thioester group, anamido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group, a nitro group ora hydroxyl group.

[0043] In the present invention, further, the transition metal compoundrepresented by the formula (I) is preferably a transition metal compoundrepresented by the following formula (I-b):

[0044] wherein M is a transition metal atom of Group 3 to Group 11 ofthe periodic table,

[0045] m is an integer of 1 to 6,

[0046] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a hydrocarbon-substitutedsilyl group, an alkoxy group, an aryloxy group, an ester group, an amidogroup, an amino group, a sulfonamido group, a cyano group or a nitrogroup, and two or more of them may be bonded to each other to form aring, and

[0047] when m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other.

[0048] In the formula (I-b), R⁶ is preferably a halogen atom, ahydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxygroup, an aryloxy group, an ester group, an amido group, an amino group,a sulfonamido group, a cyano group or a nitro group.

[0049] It is preferred that M in the transition metal compound (A) is atleast one transition metal atom selected from Groups 3 to 5 and Group 9of the periodic table.

[0050] The first olefin polymerization catalyst according to theinvention may further comprise a carrier (C), in addition to thetransition metal compound (A) and at least one compound (B) selectedfrom the organometallic compound (B-1), the organoaluminum oxy-compound(B-2) and the compound (B-3) which reacts with the transition metalcompound (A) to form an ion pair.

[0051] The first process for olefin polymerization according to thepresent invention comprises polymerizing or copolymerizing an olefin inthe presence of the above-mentioned olefin polymerization catalyst.

[0052] The second olefin polymerization catalyst according to thepresent invention comprises:

[0053] (A′) a transition metal compound represented by the followingformula (II), and

[0054] (B) at least one compound selected from:

[0055] (B-1) an organometallic compound,

[0056] (B-2) an organoaluminum oxy-compound, and

[0057] (B-3) a compound which reacts with the transition metal compound(A′) to form an ion pair.

[0058] wherein M is a transition metal atom of Group 3 to Group 11 ofthe periodic table,

[0059] R¹ to R¹⁰ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two car moreof them may be bonded to each other to form a ring,

[0060] n is a number satisfying a valence of M,

[0061] X is; a hydrogen atom, a halogen atom, a hydrocarbon group, an,oxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, arid when n is 2 or greater, plural groups X maybe the same or different and may be bonded to each other to form a ring,and

[0062] Y is a divalent bonding group containing at least one elementselected from the group consisting of oxygen, sulfur, carbon, nitrogen,phosphorus, silicon, selenium tin and boron, and when it is ahydrocarbon group, the hydrocarbon group has 3 or more carbon atoms.

[0063] In the above formula (II), at least one of R⁶ and R¹⁰ ispreferably a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group.

[0064] The transition metal compound represented by the formula (II) ispreferably a transition metal compound represented by the followingformula (II-a).

[0065] wherein M is a transition metal atom of group 3 to Group 11 ofthe periodic table,

[0066] R¹ to R¹⁰ may be the same or different, they are each a hydrogenatom, a halogen atom, a hydrocarbon group, a hydrocarbon-substitutedsilyl group, an alkoxy group, an aryloxy group, an ester group, an amidogroup, an amino group, a sulfonamido group, a cyano group or a nitrogroup, and two or more of them may be bonded to each ocher to form aring,

[0067] n is a number satisfying a valence of M,

[0068] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group or asilicon-containing group, and when n is 2 or greater, plural groups Xmay be the same or different and may be bonded to each other to form aring, and

[0069] Y is a divalent bonding group containing at least one elementselected from the group consisting of oxygen, sulfur, carbon, nitrogen,phosphorus, silicon, selenium, tin and boron, and when it is ahydrocarbon group, the hydrocarbon group has 3 or more carbon atoms.

[0070] In the above formula (II-a), at least one of R⁶ and R¹⁰ ispreferably a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group,an ester group, an amido group, an amino group, a sulfonamido group, acyano group or a nitro group.

[0071] It is preferred that M in the transition metal compound (A′) isat least one transition metal atom from Groups 4 and 5 of the periodictable.

[0072] The second olefin polymerization catalyst according to theinvention may further comprise a carrier (C), in addition to thetransition metal compound (A′) and at least one compound (B) selectedfrom the organometallic compound (B-1), the organoaluminum oxy-compound(B-2) and the compound (B-3) which reacts with the transition metalcompound (A′) to form an ion pair.

[0073] The second process for olefin polymerization comprisespolymerizing or copolymerizing an olefin in the presence of theabove-mentioned olefin polymerization catalyst.

[0074] The novel transition metal compound according to the presentinvention is represented by the following formula (III):

[0075] wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table,

[0076] m is an integer of 1 to 3,

[0077] R¹ is a hydrocarbon group, a hydrocarbon-substituted silyl group,a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an ester group, a thioestergroup, a sulfonester group or a hydroxyl group,

[0078] R² to R⁵ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an ester group, a thioestergroup, an amido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group, a nitro group, acarboxyl group, a sulfo group, a mercapto group or a hydroxyl group,

[0079] R⁶ is a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, an ester group, a thioester group, an amido group, animido group, an imino group, a sulfonester group, a sulfonamido group ora cyano group,

[0080] two or more of R¹ to R⁶ may be bonded to each other to form aring,

[0081] when m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other,

[0082] n is a number satisfying a valence of M, and

[0083] X is a halogen atom, a hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group, aboron-containing group, an aluminum-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, a silicon-containing group, a germanium-containinggroup or a tin-containing group, and when n is 2 or greater, pluralgroups X may be the same or different and may be bonded to each other toform a ring.

[0084] The above-mentioned transition metal compound is preferably acompound represented by the following formula (III-a):

[0085] wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table,

[0086] m is an integer of 1 to 3,

[0087] R¹ to R⁵ may be the same or different, and are each a hydrocarbongroup, an alkoxy group or a hydrocarbon-substituted silyl group,

[0088] R⁶ is a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, a alkylthio groupor a cyano group,

[0089] two or more of R¹ to R⁶ may be bonded to each other to form aring,

[0090] when m is 2 or greater, two groups of the groups R¹ to R⁶ may bebonded to each other, with the proviso that the groups R¹ are not bondedto each other,

[0091] n is a number satisfying a valence of M, and

[0092] X is a halogen atom, a hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group, ahalogen-containing group or a silicon-containing group, and when n is 2or greater, plural groups X may be the same or different and may bebonded to each other to form a ring.

[0093] In the formula (III-a), m is preferably 2.

[0094] The third olefin polymerization catalyst according to the presentinvention comprises:

[0095] (A″) a novel transition metal compound as described above, and

[0096] (B) at least one compound selected from:

[0097] (B-1) an organometallic compound,

[0098] (B-2) an organoaluminum oxy-compound, and

[0099] (B-3) a compound which reacts with the transition metal compound(A) to form an ion pair.

[0100] The third olefin polymerization catalyst according to the presentinvention may further comprise a carrier (C) in addition to thetransition metal compound (A″) and at least one compound (B) selectedfrom the organometallic compound (B-1), the organoaluminum oxy-compound(B-2) and the compound (B-3) which reacts with the transition metalcompound (A″) to form an ion pair.

[0101] The third process for olefin polymerization comprisespolymerizing or copolymerizing an olefin in the presence of theabove-mentioned olefin polymerization catalyst.

[0102] The α-olefin/conjugated diene copolymer according to the presentinvention is an α-olefin/conjugated diene copolymer having a molecularweight distribution (Mw/Mn) of not more than 3.5, a content ofconstituent units derived from an α-olefin in the range of 1 to 99.9% bymol and a content of constituent units derived from a conjugated dienein the range of 99 to 0.1% by mol, in which the polymer chain contains1,2-cyclopentane skeleton derived from the conjugated diene in an amountof not more than 1% by mol, and preferably the polymer chain does notsubstantially contain the 1,2-cyclopentane skeleton.

[0103] In the α-olefin/conjugated diene copolymer according to theinvention, it is preferred that the content of the constituent unitsderived from the α-olefin is in the range of 50 to 99.9% by mol and thecontent of the constituent units derived from the conjugated diene is inthe range of 50 to 0.1% by mol.

[0104] In the α-olefin/conjugated diene copolymer according to theinvention, it is preferred that the α-olefin is ethylene and/orpropylene and the conjugated diene is butadiene and/or isoprene.

BRIEF DESCRIPTION OF THE DRAWINGS

[0105]FIG. 1 shows steps for preparing the first olefin polymerizationcatalyst according to the invention.

[0106]FIG. 2 shows steps for preparing the second olefin polymerizationcatalyst according to the invention.

[0107]FIG. 3 shows the structure of transition metal compound A-1prepared in Synthesis Example 1, which was determined by X-ray structureanalysis.

[0108]FIG. 4 shows the structure of transition metal compound B-1prepared in Synthesis Example 2, which was determined by X-ray crystalstructure analysis.

DETAILED DESCRIPTION OF THE INVENTION

[0109] The olefin polymerization catalyst of the present invention andthe process for olefin polymerization using the catalyst are describedin detail hereinafter.

[0110] The meaning of the term “polymerization” used herein is notlimited to “homopolymerization” but may comprehend “copolymerization”.Also, the meaning of the term “polymer” used herein is not limited to“homopolymer” but may comprehend “copolymer”.

First Olefin Polymerization Catalyst

[0111] The first olefin polymerization catalyst of the invention isformed from:

[0112] (A) a transition metal compound represented by thebelow-described formula (I), and

[0113] (B) at least one compound selected from:

[0114] (B-1) an organometallic compound,

[0115] (B-2) an organoaluminum oxy-compound, and

[0116] (B-3) a compound which reacts with the transition metal compound(A) to form an ion pair.

[0117] First, the catalyst components for forming the olefinpolymerization catalyst of the invention are described.

[0118] (A) Transition Metal Compound

[0119] The transition metal compound (A) for use in the invention is acompound represented by the following formula (I).

[0120] In the formula (I),M is a transition metal atom of Group 3 toGroup 11 of the periodic table (Group 3 includes lantanoids), preferablyGroups 3 to 9 (Group 3 includes lantanoids), more preferably Group 3 toGroup 5 and Group 9, and particularly preferably Groups 4 or 5. SpecificExamples of transition metal atoms M include scandium, titanium,zirconium, hafnium, vanadium, niobium, tanthalum, cobalt, rhodium,yttriumn, chromium, molybdenum, tungsten, mangafese, rhenium, iron andruthenium. Of these, preferred are scandium, titanium, zirconium,hafnium, vanadium, niobium, tanthalum, cobalt and rhodium; morepreferred are titanium, zirconium, hafnium, vanadium, niobium,tanthalum, cobalt and rhodium; and particularlly prefereed are titanium,zirconium and hafnium.

[0121] m is an integer of 1 to 6, preferably 1 to 4.

[0122] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, an. oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring,

[0123] The halogen atom is fluorine, chlorine, bromine or iodine.

[0124] Examples of the hydrocarbon groups include straight-chain orbranched alkyl groups of 1 to 30, preferably 1 to 20 carbon atoms, suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, neopentyl and n-hexyl;

[0125] straight-chain or branched alkenyl groups of 2 to 30, preferably2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl;

[0126] straight-chain or branched alkynyl groups of 2 to 30, preferably2 to 20 carbon atoms, such as ethynyl and propargyl;

[0127] cyclic saturated hydrocarbon groups of 3 to 30, preferably 3 to20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and adamantyl;

[0128] cyclic unsaturated hydrocarbon groups of 5 to 30, preferably 5 to20 carbon atoms, such as cyclopentadienyl, indenyl and fluorenyl; and

[0129] aryl groups of 6 to 30, preferably 6 to 20 carbon atoms, such asphenyl, benzyl, naphthyl, biphenyl and terphenyl.

[0130] The hydrocarbon groups may be substituted with halogen atoms andfor such examples halogenated hydrocarbon groups of 1 to 30, preferably1 to 20 carbon atoms, such as trifluoromethyl, pentafluorophenyl andcholophenyl may be mentioned.

[0131] The hydrocarbon groups may also be substituted with otherhydrocarbon groups and for such examples aryl-substituted alkyl groupssuch as benzyl and cumyl may be mentioned.

[0132] Further, the hydrocarbon groups may have heterocyclic compoundresidues; oxygen-containing groups such as alkoxy, aryl, ester, ether,acyl, carboxyl, carbonate, hydroxy, peroxy and carboxylic acid anhydridegroups; nitrogen-containing groups such as ammonium salts of amino,imino, amide, imide, hydrazino, hydrazono, nitro, nitroso, cyano,isocyano, cyanic acid ester, amidino and diazo groups; boron-containinggroups such as borandiyl, borantriyl and diboranyl groups;sulfur-containing groups such as mercapto, thioester, dithioester,alkylthio, arylthio, thioacyl, thioether, thiocyanic acid ester,isothiocyanic acid ester, sulfon ester, sulfon amide, thiocarboxyl,dithiocarboxyl, sulfo, sulfonyl, sulfinyl and sulfenyl groups;phosphorus-containing groups such as phosphido, phosphoryl,thiophosphoryl and phosphate groups; silicon-containing groups;germanium-containing groups; and tin-containing groups.

[0133] Of these, particularly preferable are straight-chain or branchedalkyl groups of 1 to 30, preferably 1 to 20 carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, neopentyl and n-hexyl; aryl groups of 6 to 30, preferably 6to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl,phenanthryl and antracenyl; and these aryl groups which are substitutedwith 1 to 5 substituents such as alkyl or arkoxy groups of 1 to 30,preferably 1 to 20 carbon atoms, aryl or aryloxy groups of 6 to 30,preferably 6 to 20 carbon atoms.

[0134] Examples of nitrogen-containing groups, boron-containing groups,sulfur-containing groups and phosphorus-containing groups are thoseexemplified above.

[0135] Examples of the heterocyclic residues include those ofnitrogen-containing compounds (e.g., pyrrole, pyridine, pyrimidine,quinoline and triazine), oxygen-containing compounds (e.g., furan andpyran) and sulfur-containing compounds (e.g., thiophene), and theseheterocyclic residues, which are substituted with substituents such asalkyl or alkoxy groups of 1 to 20 carbon atoms.

[0136] Examples of the silicon-containing groups include silyl, siloxy,hydrocarbon-substituted silyl groups such as methylsilyl, dimethylsilyl,trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl,diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl,dimethyl-t-butylsilyl and dimethyl(pentafluorophenyl)silyl, preferablymethylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl,triethylsilyl and triphenylsilyl, particularly preferablytrimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl,and hydrocarbon-substituted siloxy groups such as trimethylsiloxy.

[0137] The germanium-containing groups and the tin-containing groupsinclude the above-mentioned silicon-containing groups in which siliconis replaced by germanium and tin, respectively.

[0138] The more specific illustration on the above R¹ to R⁶ is givenbelow.

[0139] Examples of the alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy and tert-butoxy.

[0140] Examples of the alkylthio groups include methylthio andethylthio.

[0141] Examples of the aryloxy groups include phenoxy,2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy.

[0142] Examples of the arylthio groups include phenylthio,methylphenylthio and naphthylthio.

[0143] Examples of the acyl groups include formyl, acyl, benzoyl,p-chlorobenzoyl and p-methoxybenzoyl.

[0144] Examples of the ester groups include acetyloxy, benzoyloxy,methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.

[0145] Examples of the thioester groups include acetylthio, benzoylthio,methylthiocarbonyl and phenylthiocarbonyl.

[0146] Examples of the amido groups include acetamido, N-methylacetamidoand N-methylbenzamido.

[0147] Examples of the imido groups include acetimido and benzimido.

[0148] Examples of the amino groups include dimethylamino,ethylmethylamino and diphenylamino.

[0149] Examples of the imino groups include methylimino, ethylimino,propylimino, butylimino and phenylimino.

[0150] Examples of the sulfonester groups include methylsulfonato,ethylsulfonato and phenylsulfonato.

[0151] Examples of the sulfonamido groups include phenylsulfonamido,N-methylsulfonamido and N-methyl-p-toluenesulfonamido.

[0152] R⁶ is preferably a substituent other than hydrogen. That is, ahydrogen atom, a halogen atom, a hydrocarbon group, a heterocycliccompound residue, an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorous-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring. R⁶ is particularlypreferably a halogen atom, a hydrocarbon group, a heterocyclic compoundresidual group, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group.

[0153] Preferred examples of the hydrocarbon groups available as R⁶include straight-chain or branched alkyl groups of 1 to 30, preferably 1to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl; cyclic Saturatedhydrocarbon groups of 3 to 30, preferably 3 to 20 carbon atoms, such ascyclopropanyl, cyclobutanyl, cyclopentanyl, cyclohexyl and adamantyl;aryl groups of 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl,benzyl, naphthyl, biphenyl and terphenyl; and these groups which aresubstituted with substituents such as alkyl or alkoxy groups of 1 to 30,preferably 1 to 20 carbon atoms, halogenated alkyl groups of 1 to 30,preferably 1 to 20 carbon atoms, aryl or alkoxy groups of 6 to 30,preferably 6 to 20 carbon atoms, halogen, cyano, nitro and hydroxyl.

[0154] Preferred examples of the hydrocarbon-substituted silyl groups asR⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,dimethylphenylsilyl, dimethyl-t-butylsilyl anddimethyl(pentafluorophenyl)silyl. Particularly preferable aretrimethylsilyl, triphenylsilyl, diphenylmethylsilyl, isophenylsilyl,dimethylphenylsilyl, dimethyl-t-butylsilyl anddimethyl(pentafluorophenyl)silyl.

[0155] In the present invention, R⁶ is a preferably selected frombranched alkyl groups of 3 to 30, preferably 3 to 20 carbon atoms (e.g.,isopropyl, isobutyl, sec-butyl and tert-butyl neopentyl), these alkylgroups which are substituted with aryl groups of 6 to 30, preferably 6to 20 carbon atoms (e.g., cumyl), and cyclic saturated hydrocarbongroups of 3 to 30, preferably 3 to 20 carbon atoms (e.g., adamantyl,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl).

[0156] Also, preferable R⁶ is an aryl group of 6 to 30, preferably 6 to20 carbon atoms (e.g., phenyl, naphthyl, fluorenyl, anthranyl orphenanthryl) or a hydrocarbon-substituted silyl group.

[0157] Two or more of the groups R¹ to R^(6,) preferably adjacentgroups, may be bonded to each other to form an aliphatic ring, anaromatic ring or a hydrocarbon ring containing a hetero atom such as anitrogen atom, and these rings may further have a substituent.

[0158] When m is 2 or greaser, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other. R¹s, R²s, R³s, R⁴s, R⁵s, or R⁶s may be the same as ordifferent from each other.

[0159] n is a number satisfying a valence of M, specifically an integerof 0 to 5, preferably 1 to 4, more preferably 1 to 3.

[0160] X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring.

[0161] Examples of the halogen atom include fluorine, chlorine, bromineand iodine.

[0162] Examples of the hydrocarbon groups include those exemplified forR¹ to R⁶. Specifically, there can be mentioned, but not limited to,alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl,dodecyl and eicosyl; cycloalkyl groups of 3 to 30 carbon atoms, such ascyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups, suchas vinyl, propenyl and cyclohexenyl; arylalkyl groups, such as benzyl,phenylethyl and phenylpropyl; and aryl groups, such as phenyl, tolyl,dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,naphthyl, methylnaphthyl, anthryl and phenanthryl.

[0163] These hydrocarbon groups include halogenated hydrocarbon groups,and more specifically at least one hydrogen of the hydrocarbon groups of1 to 30 carbon atoms may be substituted with a halogen atom.

[0164] Of these, preferable are chose of 1 to 20 carbon atoms.

[0165] Examples of the heterocyclic compound residues include thoseexemplified for R¹ to R⁶

[0166] Examples of the oxygen-containing groups include thoseexemplified for R¹ to R⁶. Specificatlly, there can be mentioned, but notlimited to, hydroxyl; alkoxy groups, such as methoxy, ethoxy, propoxyand butoxy; aryloxy groups, such as phenoxy, methylphenoxy,dimethylphenoxy and naphthoxy; arylalkoxy groups, such as phenylmethoxyand phenylethoxy; acetoxy groups; and carbonyl group.

[0167] Examples of the sulfur-containing groups include thoseexemplified for R¹ to R⁶. Specifically, there can be mentioned, but notlimited to, sulfonato groups, such as methylsulfonato,trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato,p-toluenesulfonato, trimethylbenzenesulfonato,triisobutylbenzenesulfonato, p-chlorobenzenesulfonato andpentafluorobenzenesulfonato; sulfinato groups, such as methylsulfinato,phenylsulfinato, benzylsulfinato, p-toluenesulfonato,trimethylbenzenesulfinato and pentafluorobenzenesulfinato; alkylthiogroups; and arylthio groups.

[0168] Examples of the nitrogen-containing groups include thoseexemplified for R¹ to R⁶. Specifically, there can be mentioned, but notlimited to, amino group; alkylamino groups, such as methyl amino,dimethylamino; diethylamino; dipropylamino, dibutylamino anddicyclohexylamino; arylamino groups and alkylarylamino groups, such asphenylamino, diphenylamino, ditolylamino, dinaphthylamino andmethylphenylamino.

[0169] Examples of the boron-containing groups include BR₄ groups (whereR is a hydrogen, an aryl group which may have a substituent, a halogen,etc.).

[0170] Examples of the silicon-containing groups include thoseexemplified for R¹ to R⁶. Specifically, there can be mentioned, but notlimited to, hydrocarbon-substituted silyl groups, such as phenylsilyl,diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl,tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyland trinaphthylsilyl; hydrocarbon-substituted silylether groups, such astrimethylsilylether; silicon-substituted alkyl groups, such astrimethylsilylmethyl; and silicon-substituted aryl groups, such astrimethylsilylphenyl.

[0171] Examples of the germanium-containing groups include thoseexemplified for R¹ to R⁶. Specifically, there can be mentioned theabove-mentioned silicon-containing groups in which silicon is replacedby germanium.

[0172] Examples of the tin-containing groups include those exemplifiedfor R¹ to R⁶. Specifically, there can be mentioned the above-mentionedsilicon -containing groups in which silicon is replaced by tin.

[0173] Examples of the halogen-containing groups includefluorine-containing groups, such as PF₆ and BF₄; chlorine-containinggroups, such as ClO₄ and SbCl₆; and iodine-containing groups, such asIO₄, but not limited thereto.

[0174] Examples of the aluminium-containing groups include AR₄ groups(where R is a hydrogen, an alkyl group, an aryl group which may have asubstituent, a halogen atom, etc.), but not limited thereto.

[0175] When n is 2 or greater, plural groups X may be the same ordifferent and may be bonded to each other to form a ring.

[0176] Transition metal compound (I-a)

[0177] The transition compound represented by the formula (I) ispreferably a compound represented by the formula (I-a).

[0178] In the formula (I-a), M is a transition metal atom of Group 3 toGroup 11 of the periodic table. Examples of M include theabove-mentioned transition metal atoms.

[0179] m is an integer of 1 to 3, preferably 2.

[0180] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidues, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group, a caroboxyl group, a sulfo group, a mercapto groupor a hydroxyl group, and two or more of them may be bonded to each otherto form a ring. Examples of R¹ to R⁶ include those described above.

[0181] When m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other.

[0182] n is a number satisfying a valence of M, specifically an integerof 0 to 5, preferably 1 to 4, more preferably 1 to 3.

[0183] X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group. Examples of X include those described above.

[0184] When n is 2 or greater, plural groups X may be the same ordifferent and may be bonded to each other to form a ring.

[0185] The transition metal compound represented by the formula (I) ispreferably a compound represented by the following formula (I-a-1).

[0186] In the formula (I-a-1), R¹ to R⁶, M and X have the same meaningsas mentioned above, and are preferably those described below.

[0187] M is a transition metal atom of Group 3 to Group 11 of theperiodic table, preferably of Group 3 to Group 5 and Group 9, e.g.,scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum,cobalt or rhodium, more preferably titanium, zirconium, hafnium, cobaltor rhodium, particularly preferably titanium, zirconium or hafnium.

[0188] m is an integer of 1 to 3.

[0189] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidues, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, a thioester group, an estergroup, an acyl group, an amido group, an imido group, an amino group, animino group, a sulfonester group, a sulfonamido group, a cyano group, anitro group or a hydroxyl group. Of these, particularly preferable is ahydrogen atom, a halogen atom, a hydrocarbon-substituted silyl group, analkoxy group, an aryloxy group, an ester group, an amido group, an aminogroup, a sulfonamido group, a cyano group or a nitro group.

[0190] Examples of the halogen atom include fluorine, chlorine, bromineand iodine.

[0191] Examples of the hydrocarbon groups include straight-chain orbranched alkyl groups of 1 to 20 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyland hexyl; straight-chain or branched alkenyl groups of 2 to 20 carbonatoms, such as vinyl, allyl and isopropenyl; straight-chain or branchedalkynyl groups of 2 to 20 carbon atoms, such as ethynyl and propargyl;cyclic saturated hydrocarbon groups of 3 to 20 carbon atoms, such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; arylgroups of 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl,biphenylyl and triphenylyl; cyclic unsaturated hydrocarbon groups of 5to 20 carbon atoms, such as cyclopentadienyl, indenyl and fluorenyl; andthese groups which are substituted with substituents such as alkylgroups of 1 to 20 carbon atoms, halogenated alkyl groups of 1 to 20carbon atoms, aryl groups of 6 to 20 carbon atoms, alkoxy groups of 1 to20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms, halogen, cyano,nitro and hydroxyl. Of these, particularly preferable are straight-chainor branched alkyl groups of 1 to 20 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyland hexyl; aryl groups of 6 to 20 carbon atoms, such as phenyl andnaphthyl; and these aryl groups which are substituted with 1 to 5substituents such as alkyl groups of 1 to 20 carbon atoms, aryl groupsof 6 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms andaryloxy groups of 6 to 20 carbon atoms.

[0192] Examples of the heterocyclic residues include residues ofnitrogen-containing compounds (e.g., pyrrole, pyridine, pyrimidine,quinoline and triazine), oxygen-containing compounds (e.g., furan andpyran) and sulfur-containing compounds (e.g., thiophene), and theseheterocyclic residues which are substituted with substituents such asalkyl groups and alkoxy groups fo 1 to 20 carbon atoms.

[0193] Examples of the hydrocarbon-substituted silyl groups includemethylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl,triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl,dimethyl-t-butylsilyl and dimethyl(pentafluorophenyl)silyl. Of these,particularly preferable are methylsilyl, dimethylsilyl, trimethylsilyl,ethylsilyl, diethylsilyl, triethylsilyl and triphenylsilyl.

[0194] Examples of the hydrocarbon-substituted siloxy groups includetrimethylsiloxy.

[0195] Examples of the alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy and tert-butoxy.

[0196] Examples of the alkylthio groups include methylthio andethylthio.

[0197] Examples of the aryloxy groups include phenoxy,2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy.

[0198] Examples of the arylthio groups include phenylthio,methylphenylthio and naphthylthio.

[0199] Examples of the acyl groups include formyl, acetyl, benzoyl,p-chlorobenzoyl and p-methoxybenzoyl.

[0200] Examples of the ester groups include acetyloxy, benzoyloxy,methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.

[0201] Examples of the thioester groups include acetylthio, benzoylthio,methylthiocarbonyl and phenylthiocarbonyl.

[0202] Examples of the amido groups include acetamido, N-methylacetamidoand N-methylbenzamido.

[0203] Examples of the imido groups include acetimido and benzimido.

[0204] Examples of the amino groups include dimethylamino,ethylmethylamino and diphenylamino.

[0205] Examples of the imino groups include methylimino, ethylimino,propylimino, butylimino and phenylimino.

[0206] Examples of the sulfonester groups include methylsulfonato,ethylsulfonato and phenylsulfonato.

[0207] Examples of the sulfonamido groups include phenylsulfonamido,N-methylsulfonamido and N-methyl-p-toluenesulfonamido.

[0208] R⁶ is preferably a substituent other than hydrogen. That is, R⁶is preferably a halogen atom, a hydrocarbon group, a heterocycliccompound residues, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group.

[0209] Preferred examples of the hydrocarbon groups as R⁶ includestraight-chain or branched alkyl groups of 1 to 20 carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl and hexyl; cyclic saturated hydrocarbon groups of 3to 20 carbon atoms, such as cyclopropyl, cyclobutnyl, cyclopentyl,cyclohexyl and adamantyl; aryl groups of 6 to 20 carbon atoms, such asphenyl, benzyl, naphthyl, biphenylyl and triphenylyl; and these groupswhich are substituted with substituents such as alkyl groups of 1 to 20carbon atoms, halogenated alkyl groups of 1 to 20 carbon atoms, arylgroups of 6 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms,aryloxy groups of 6 to 20 carbon atoms, halogen, cyano, nitro andhydroxyl.

[0210] Preferred examples of the hydrocarbon-substituted silyl groups asR⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,dimethylphenylsilyl, dimethyl-t-butylsilyl anddimethyl(pentafluorophenyl)silyl.

[0211] In the present invention, R⁶ is preferably selected from branchedalkyl groups of 3 to 20 carbon atoms (e.g., isopropyl, isobutyl,sec-butyl and tert-butyl), these alkyl groups which are substituted witharyl groups of 6 to 20 carbon atoms (e.g., cumyl), and cyclic saturatedhydrocarbon groups of 3 to 20 carbon atoms (e.g., adamantyl,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl). Also, preferableR⁶ is a hydrocarbon-substituted silyl group.

[0212] Two or more groups R¹ to R^(6,) preferably adjacent groups, maybe bonded to each other to form an aliphatic ring, an aromatic ring or ahydrocarbon ring containing a hetero atom such as a nitrogen atom, andthese rings may further have a substituent.

[0213] When m is 2 or greater, two of the the groups R¹ to R⁶ may bebonded to each other, with the proviso that the groups R¹ are not bondedto each other. R¹s, R²s, R³s, R⁴s, R⁵s, or R⁶s may be the same as ordifferent from each other.

[0214] n is a number satisfying a valence of M, specifically an integerof 1 to 3.

[0215] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group or asilicon-containing group, and when n is 2 or greater, plural groups Xmay be the same or different.

[0216] Examples of the he halogen atoms include fluorine, chlorine,bromine and iodine.

[0217] Examples of the hydrocarbon groups of 1 to 20 carbon atomsinclude alkyl groups, cycloalkyl groups, alkenyl groups, arylalkylgroups and aryl groups. Specifically, there can be mentioned alkylgroups, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl,dodecyl and eicosyl; cycloalkyl groups, such as cyclopentyl, cyclohexyl,norbornyl and adamantyl; alkenyl groups, such as vinyl, propenyl andcyclohexenyl; arylalkyl groups, such as benzyl, phenylethyl andphenylpropyl; and aryl groups, such as phenyl, tolyl, dimethylphenyl,trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,methylnaphthyl, anthryl and phenanthryl.

[0218] Examples of the halogenated hydrocarbon groups of 1 to 20 carbonatoms include the above-mentioned hydrocarbon groups of 1 to 20 carbonatoms which are substituted with halogens.

[0219] Examples of the oxygen-containing groups include hydroxyl; alkoxygroups, such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups,such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; andarylalkoxy groups, such as phenylmethoxy and phenylethoxy.

[0220] Examples of the sulfur-containing groups include theabove-exemplified oxygen-containing groups in which oxygen is replacedwith sulfur; sulfonato groups, such as methylsulfonato,trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato,p-toluenesulfonato, trimethylbenzenesulfonato,triisobutylbenzenesulfonato, p-chlorobenzenesulfonato andpentafluorobenzenesulfonato; and sulfinato groups, such asmethylsulfinato, phenylsulfinato, benzylsulfinato, p-toluenesulfinato,trimethylbenzenesulfinato and pentafluorobenzenesulfinato.

[0221] Examples of the silicon-containing groups includemonohydrocarbon-substituted silyl groups, such as methylsilyl andphenylsilyl; dihydrocarbon-substituted silyl groups, such asdimethylsilyl and diphenylsilyl; trihydrocarbon-substituted silylgroups, such as trimethylsilyl, triethylsilyl, tripropylsilyl,tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl,methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethergroups of hydrocarbon-substituted silyl, such as trimethylsilyl ether;silicon-substituted alkyl groups, such as trimethylsilylmethyl; andsilicon-substituted aryl groups, such as trimethylsilylphenyl.

[0222] Of these, preferable groups X are halogen atoms, hydrocarbonatoms of 1 to 20 carbon atoms and sulfonato groups.

[0223] When n is 2 or greater, groups X may be bonded to each other toform a ring.

[0224] Of the transition metal compounds represented by the formula(I-a-1), the compound wherein m is 2 and two of the groups R¹ to R⁶(except for the groups R¹) are bonded to each other is, for example, acompound represented by the following formula (I-a-2).

[0225] In the formula (I-a-2), M, R¹ to R⁶, and X are identical with M,R¹ to R⁶, and X in the formula (I).

[0226] R¹ to R¹⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup or a nitro group, specifically, the same atom or group asdescribed for R¹ to R⁶. Two or more of groups R¹ to R^(16,) preferablyadjacent groups, may be bonded to each other to form an aliphatic ring,an aromatic ring or a hydrocarbon ring containing a hetero atom such asa nitrogen atom.

[0227] Y′ is a bonding group or a single bond for bonding at least onegroup selected from R¹ to R⁶ to at least one group selected from R¹¹ toR¹⁶ (except a case of bonding R¹ and R¹¹ to each other).

[0228] The bonding group Y′ is a group containing at least one elementselected from among oxygen, sulfur, carbon, nitrogen, phosphorus,silicon, selenium, tin, boron and the like. Examples of such groupsinclude groups containing chalcogen atoms such as —O—, —S— and —Se—;nitrogen- or phosphorus-containing groups, such as —NH—, —N(CH₃)₂, —PH—and —P(CH₃)₂—; hydrocarbon groups of 1 to 20 carbon atoms, such as—CH₂—, —CH₂—CH₂— and —C(CH₃)₂—; residues of cyclic unsaturatedhydrocarbons of 6 to 20 carbon atoms, such as benzene, naphthalene andanthracene; residues of heterocyclic compounds having 3 to 20 carbonatoms and containing hetero atoms, such as pyridine, quinoline,thiophene and furan; silicon atom-containing groups, such as —SiH₂— and—Si(CH₃)₂; tin atom-containing groups, such as —SiH₂— and —Sn(CH₃)₂; andboron atom-containing groups, such as —BH—, —B(CH₃)— and —BF—.

[0229] Examples of the transition metal compounds represented by theformula (I-a-1) are given below, but are not limited thereto.

[0230] In the following examples, M is a transition metallic element,and specifically represents, but not limited to, Sc(III), Ti(III),Ti(IV), Zr(III), Zr(IV), Hf(IV), V(IV), Nb(V), Ta(V), Co(II), Co(III),Rh(II), Ph(III), Ph(IV). Of these, particularly preferable is Ti(IV),Zr(IV) or Hf(IV).

[0231] X is halogen such as Cl or Br, or an alkyl group such as methyl,but not limited thereto. When plural X are present, they may be the sameor different.

[0232] n depends on a valence of the metal M. For example, when twomonoanion species are bonded to the metal, n=0 in case of a divalentmetal, n=1 in case of a trivalent metal, n=2 in case of a tetravalentmetal, and n=3 in case of a pentavalent metal. More specifically, therecan be mentioned n=2 in case of Ti(IV), n=2 in case of Zr(IV), and n=2in case of Hf(IV).

[0233] In the above chemical formulae, Me is methyl, Et is ethyl, iPr isisopropyl, tBu is tert-butyl and Ph is phenyl.

[0234] More specific examples of compounds having a center metal Ti aregiven below. There can also be mentioned those compounds in whichtitanium is replaced with zirconium, hafnium, cobalt or rhodium.

[0235] In the olefin polymerization catalyst according to the invention,it is particularly preferable to use a novel transition metal compoundof the formula (III), which will be described in detail below, as thecatalyst component (A′).

[0236] Transition metal compound (I-b)

[0237] Also employable as the transition metal compound (A) in theinvention is a transition metal compound represented by the followingformula (I-b).

[0238] In the formula (I-b), M is a transition metal atom of Group 3 toGroup 11 of the periodic table, preferably of Group 4 or Group 9, andparticularly preferably, titanium, zirconium, hafnium, cobalt orrhodium.

[0239] m is an integer of 1 to 6, preferably 1 to 4.

[0240] R¹ to R⁶ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a hydrocarbon-substitutedsilyl group, an alkoxy group, an aryloxy group, an ester group, an amidogroup, an amino group, a sulfonamido group, a cyano group or a nitrogroup.

[0241] Of these, particularly preferable is a halogen atom, ahydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxygroup, an aryloxy group, an ester group, an amido group, an amino group,a sulfonamido group, a cyano group or a nitro group.

[0242] Examples of the groups R¹ to R⁶ are those exemplified for thetransition metal compounds of the formulae (I) and (I-a).

[0243] When m is 2 or greater, two or more groups R¹ to R⁶, preferablyadjacent groups, may be bonded to each other to form a ring, with theproviso that the groups R¹ are not bonded to each other.

[0244] Examples of the transition metal compounds represented by theformula (I-b) are given below, but not limited thereto.

[0245] In the present invention, transition metal compounds whereincobalt is replaced with titanium, zirconium, hafnium, iron, copper orrhodium in the above-exemplified compounds are also employable.

[0246] The transition metal compounds (A) mentioned above are usedsingly or in combination of two or more kinds, and they can be used incombination with other transition metal compounds, for example knowntransition metal compounds comprising a ligand which has a hetero atomsuch as nitrogen, oxygen, sulfur, boron or phosphorus.

[0247] Other transition metal compound

[0248] Some examples of the other transition metal compounds are givenbelow, but the compounds are not limited those examples.

[0249] (a-1) Transition metal imide compound (I-c)

[0250] In the above formula, M is a transition metal atom of Group 8 toGroup 10 of the periodic table, preferably nickel, palladium orplatinum.

[0251] R²¹ to R²⁴ may be the same or different, and are each ahydrocarbon group of 1 to 50 carbon atoms, a halogenated hydrocarbongroup of 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, ora hydrocarbon group substituted with a substituent containing at leastone element selected from nitrogen, oxygen, phosphorus, sulfur andsilicon.

[0252] Two or more groups, preferably adjacent groups, of R²¹ to R²⁴ maybe bonded to each other to form a ring.

[0253] q is an integer of 0 to 4.

[0254] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group, and when q is 2or greater, plural groups X may be the same or different.

[0255] (a-2) Transition metal amide compound (I-d)

[0256] In the above formula, M is a transition metal atom of Group 3 toGroup 6 of the periodic table, preferably titanium, zirconium orhafnium.

[0257] R′ and R″ may be the same or different, and are each a hydrogenatom, a hydrocarbon group of 1 to 50 carbon atoms, a halogenatedhydrocarbon group of 1 to 50 carbon atoms, a hydrocarbon-substitutedsilyl group, or a substituent containing at least one element selectedfrom nitrogen, oxygen, phosphorus, sulfur and silicon.

[0258] m is an integer of 0 to 2.

[0259] n is an integer of 1 to 5.

[0260] A is an atom of Group 13 to Group 16 of the periodic table,specifically boron, carbon, nitrogen, oxygen, silicon, phosphorus,sulfur, germanium, selenium, tin or the like, preferably carbon orsilicon.

[0261] When n is 2 or greater, plural atoms A may be the same ordifferent.

[0262] E is a substituent containing at least one element selected fromcarbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boronand silicon. When plural groups E are present, they may be the same ordifferent, and two or more groups E may be bonded to form a ring.

[0263] p is an integer of 0 to 4.

[0264] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group. When p is 2 orgreater, plural groups X may be the same or different.

[0265] X is preferably a halogen atom, a hydrocarbon group of 1 to 20carbon atoms or a sulfonato group.

[0266] (a-3) Transition metal diphenoxy compound (I-e)

[0267] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table; 1 and m are each an integer of 0 or 1; Aand A′ are each a hydrocarbon group of 1 to 50 carbon atoms, ahalogenated hydrocarbon group of 1 to 50 carbon atoms, a hydrocarbongroup having a substituent containing oxygen, sulfur or silicon, or ahalogenated hydrocarbon group having a substituent containing oxygen,sulfur or silicon; and A and A′ may be the same or different.

[0268] B is a hydrocarbon group of 0 to 50 carbon atoms, a halogenatedhydrocarbon group of 1 to 50 carbon atoms, R¹R²Z, oxygen or sulfur,where R¹ and R² are each a hydrocarbon group of 1 to 20 carbon atoms ora hydrocarbon group having 1 to 20 carbon atoms and containing at leastone hetero atom, and Z is carbon, nitrogen, sulfur, phosphorus orsilicon.

[0269] n is a number satisfying a valence of M.

[0270] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group, and when n is 2or greater, plural groups X may the same or different and may be bondedto form a ring.

[0271] (a-4) Transition metal compound (I-f) containing at least onehetero atom and containing a ligand having cyclopentadienyl skeleton

[0272] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table. X is an atom of Group 13, Group 14 orGroup 15, and at least one of X contains an element other than carbon.

[0273] Each R may be the same or different, and is a hydrogen atom, ahalogen atom, a hydrocarbon group, a halogenated hydrocarbon group, ahydrocarbon-substituted silyl group or a hydrocarbon group substitutedwith a substituent containing at least one element selected fromnitrogen, oxygen, phosphorus, sulfur and silicon. Two or more of R maybe bonded to form a ring, and a is 0 or 1.

[0274] b is an integer of 1 to 4, when b is a number of 2 or greater,the moieties [((R) _(a))₅X₅] may be the same or different, and thegroups R may be bonded to form a bridge.

[0275] c is a number satisfying a valence of M.

[0276] Y is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group, or nitrogen-containing group. When c is anumber of 2 or greater, plural groups Y may be the same or different andmay be bonded to form a ring.

[0277] (a-5) Transition metal compound represented by the formulaRB(Pz)₃MX_(n)

[0278] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table; R is a hydrogen atom, a hydrocarbongroup of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to20 carbon atoms; and Pz is a pyrazolyl group or a substituted pyrazolylgroup.

[0279] n is a number satisfying a valence of M.

[0280] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group, and when n is anumber of 2 or greater, plural groups X may be the same or different andmay be bonded to form a ring.

[0281] (a-6) Transition metal compound represented by the followingformula (I-g)

[0282] In the above formula, Y₁ and Y₃ are each an element of Group 15of the periodic table; Y₂ is an element of Group 16 of the periodictable; and R²¹ to R²⁸ may be the same or different, they are each ahydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbonatoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, anoxygen-containing group, a sulfur-containing group or asilicon-containing group, and two or more of them may be bonded to forma ring.

[0283] (a-7) Transition metal compound comprising a compound representedby the following formula (I-h) and a transition metal atom of Group VIII

[0284] In the above formula, R³¹ to R³⁴ may be the same or different,they are each a hydrogen atom, a halogen atom, a hydrocarbon group of 1to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbonatoms, and two or more of them may be bonded to form a ring.

[0285] (a-8) Transition metal compound represented by the followingformula (I-i)

[0286] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table.

[0287] m is an integer of 0 to 3.

[0288] n is an integer of 0 or 1.

[0289] p is an integer of 1 to 3.

[0290] q is a number satisfying a valence of M.

[0291] R⁴¹ to R⁴⁸ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or ahalogenated hydrocarbon group of 1 to 20 carbon atoms, anoxygen-containing group, a sulfur-containing group, a silicon-containinggroup or nitrogen-containing group, and two or more of them may bebonded to form a ring.

[0292] X is a hydrogen atom, a hologen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group, and when q is 2or greater, plural X may be the same or different and may be bonded toeach other to form a ring.

[0293] Y is a group bridging the borata benzen ring, and Y is carbon,silicon or germanium.

[0294] A is an element of Group 14, Group 15 or Group 16 of the periodictable.

[0295] (B-1) Organometallic compound

[0296] As the organometallic compound (B-1), the below-describedorganometallic compounds of metals of Group 1, Group 2, Group 12 andGroup 13 of the periodic table are employable in the invention.

[0297] (B-1a) Organoaluminum compound represented by the followingformula:

R^(a) _(m)Al(OR^(b))_(n)H_(p)X_(q)

[0298] wherein R^(a) and R^(b) may be the same or different, and areeach a hydrocarbon group of 1 to 15 carbon atoms, preferably ahydrocarbon group of 1 to 4 carbon atoms; X is a halogen atom; and m, n,p and q are numbers satisfying the conditions of 0<m≦3, 0≦n<3, 0≦p<3,0≦q<3 and m+n+p+q=3.

[0299] (B-1b) Alkyl complex compound of Group 1 metal and aluminum, thatis represented by the following formula:

M²AlR^(a) ₄

[0300] wherein M² is Li, Na or K; and R^(a) is a hydrocarbon group of 1to 15 carbon atoms, preferably a hydrocarbon group of 1 to 4 carbonatoms.

[0301] (B-1c) Dialkyl compound of Group 2 metal or Group 12 metal, thatis represented by the following formula:

R^(a)R^(b)M³

[0302] wherein R^(a) and R^(b) may be the same or different, and areeach a hydrocarbon group of 1 to 15 carbon atoms, preferably ahydrocarbon group of 1 to 4 carbon atoms; and M³ is Mg, Zn or Cd.

[0303] Examples of the organoaluminum compounds (B-1a) include thefollowing compounds.

[0304] Organoaluminum compound represented by the following formula:

R^(a) _(m)Al(OR^(b))_(3-m)

[0305] wherein R^(a) and R^(b) may be the same or different, and areeach a hydrocarbon group of 1 to 15 carbon atoms, preferably ahydrocarbon group of 1 to 4 carbon atoms; and m is preferably a numbersatisfying the condition of 1.5≦m≦3.

[0306] Organoaluminum compound represented by the following formula:

R^(a) _(m)AlX_(3-m)

[0307] wherein R^(a) is a hydrocarbon group of 1 to 15 carbon atoms,preferably a hydrocarbon group of 1 to 4 carbon atoms; X is a halogenatom; and m is preferably a number satisfying the condition of 0≦m≦3.

[0308] Organoaluminum compound represented by the following formula:

R^(a) _(m)AlH_(3-m)

[0309] wherein R^(a) is a hydrocarbon group of 1 to 15 carbon atoms,preferably a hydrocarbon group of 1 to 4 carbon atoms; and m ispreferably a number satisfying the condition of 2≦m<3.

[0310] organoaluminum compound represented by the following formula:

R^(a) _(m)Al(OR^(b))_(n)X_(q)

[0311] wherein R^(a) and R^(b) may be the same or different, and areeach a hydrocarbon group of 1 to 15 carbon atoms, preferably ahnydrocarbon group of 1 Lo 4 carbon atoms; X is a halogen atom; and m, nand q are numbers satisfying the conditions of 0<m≦3, 0≦n<3, 0≦q<3 andm+n+q=3.

[0312] Particular examples of the organoaluminum compounds (B-1a)include:

[0313] tri-n-alkylaluminums, such as tri-methylaluminum,triethylaluminum, tri-n-butylaluminum, tripropylaluminum,tripentylaluminum, trihexylaluminum, trioctylalminum andtridecylaluminum;

[0314] branched-chain trialkylaluminums, such as triisoprcpylaluminum,triisobulylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,tri-2-menhylbutylaluminum, tri-3-methylbutylaluminum,tri-2-methylpentylaluminum, tri-3-methylpentylaluminum,tri-4-methylpentylaluminum, tri-2-methylhexylaluminum,tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum;

[0315] tricycloalkylaluminums, such as tricyclohexylaluminum andtricyclooctylaluminum;

[0316] triarylaluminums, such as triphenylaluminum and tritolylaluminum;

[0317] dialkylaluminum hydrides, such as diisobutylaluminum hydride;

[0318] trialkenylaluminums represented by the formula(i-C₄H₉)_(x)Al_(y)(C₅H₁₀)_(z) (wherein x, y and z are positive numbers,and z≧2×), such as isoprenylaluminum;

[0319] alkylaluminum alkoxides, such as isobutylaluminum methoxide,isobutylaluminum ethoxide and isobutylaluminum isopropoxide;

[0320] dialkylaluminum alkoxides, such as dimethylaluminum methoxide,diethylaluminum ethoxide and dibutylaluminum butoxide;

[0321] alkylaluminum sesquialkoxides, such as ethylaluminumsesquiethoxide and butylaluminum sesquibutoxide;

[0322] partially alkoxylated alkylaluminums having an averagecomposition represented by R^(a) _(2.5)Al(OR^(b))_(0.5);

[0323] dialkylaluminum aryloxides, such as diethylaluminum phenoxide,diethylaluminum(2,6-di-t-butyl-4-methylphenoxide),ethylaluminumbis(2,6-di-t-butyl-4-methylphenoxide),diisobutylaluminum(2,6-di-t-butyl-4-methylphenoxide) andisobutylaluminumbis(2,6-di-t-butyl-4-methylphenoxide);

[0324] dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, dibutylaluminum chloride, diethylaluminumbromide and diisobutylaluminum chloride;

[0325] alkylaluminum sesquihalides, such as ethylaluminumsesquichloride, butylaluminum sesquichloride and ethylaluminumsesquibromide, partially halogenated alkylaluminums, such asethylaluminum dichloride, propylaluminum dichloride and butylaluminumdibromide;

[0326] dialkylaluminum hydrides, such as diethylaluminum hydride anddibutylaluminum hydride;

[0327] partially hydrogenated alkylaluminums, e.g., alkylaluminumdihydrides, such as ethylaluminum dihydride and propylaluminumdihydride; and

[0328] partially alkoxylated and halogenated alkylaluminums, such asethylaluminum ethoxychloride, butylaluminum butoxychloride andethylaluminum ethoxybromide.

[0329] Also employable are compounds analogous to the organoaluminumcompound (B-1a). For example, there can be mentioned organoaluminumcompounds wherein two or more aluminum compounds are combined through anitrogen atom, such as (C₂H₅)₂AlN(C₂H₅)Al(C₂H₅)₂.

[0330] Examples of the organoaluminum compounds (B-1b) include LiAl(C₂H₅)₄ and LiAl (C₇H₁₅)₄.

[0331] Further, other compounds such as methyllithium, ethyllithium,propyllithium, butyllithium, methylmagnesium bromide, methylmagnesiumchloride, ethylmagnesium bromide, ethylmagnesium chloride,propylmagnesium bromide, propylmagnesium chloride, butylmagnesiumbromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium,dibutylmagnesium and butylethylmagnesium are also employable as theorganometallic compounds (B-1).

[0332] Furthermore, combinations of compounds capable of producing theabove-mentioned organoaluminum compounds in the polymerization system,e.g., a combination of halogenated aluminum and alkyllithium and acombination of halogenated aluminum and alkylmagnesium, are alsoemployable.

[0333] Of the organometallic compounds (B-1) mentioned above, theorganoaluminum compounds are preferable.

[0334] The organometallic compounds (B-1) can be used singly or incombination of two or more kinds.

[0335] (B-2) Organoaluminum oxy-compound

[0336] The organoaluminum oxy-compound (B-2) for use in the inventionmay be conventional aluminoxane or a benzene-insoluble organoaluminumoxy-compound exemplified in Japanese Patent Laid-Open Publication No.78687/1990.

[0337] The conventional aluminoxane can be prepared by, for example, thefollowing processes, and is generally obtained as a hydrocarbon solventsolution.

[0338] (1) An organoaluminum compound such as trialkylaluminum is addedto a hydrocarbon medium suspension of a compound containing adsorbedwater or a salt containing water of crystallization, e.g., magnesiumchloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate,nickel sulfate hydrate or cerous chloride hydrate, to allow theorganoaluminum compound to react with the adsorbed water or the water ofcrystallization.

[0339] (2) Water, ice or water vapor is allowed to directly act on anorganoaluminum compound such as trialkylaluminum in a medium such asbenzene, toluene, ethyl ether or tetrahydrofuran.

[0340] (3) An organotin oxide such as dimethyltin oxide or dibutyltinoxide is allowed to react with an organoaluminum compound such astrialkylaluminum in a medium such as decane, benzene or toluene.

[0341] The aluminoxane may contain a small amount of an organometalliccomponent. Further, it is possible that the solvent or the unreactedorganoaluminum compound is distilled off from the recovered solution ofaluminoxane and the remainder is redissolved in a solvent or suspendedin a poor solvent for aluminoxane.

[0342] Examples of the organoaluminum compounds used for preparing thealuminoxane include the same organoaluminum compounds as described forthe organoaluminum compound (B-1a).

[0343] Of these, preferable are trialkylaluminums andtricycloalkylaluminums. Particularly preferable is trimethylaluminum.

[0344] The organoaluminum compounds can be used singly or in combinationof two or more kinds.

[0345] Examples of the solvents used for preparing the aluminoxaneinclude aromatic hydrocarbons, such as benzene, toluene, xylene, cumeneand cymene; aliphatic hydrocarbons, such as pentane, hexane, heptane,octane, decane, dodecane, hexadecane and octadecane; alicyclichydrocarbons, such as cyclopentane, cyclohexane, cyclooctane andmethylcyclopentane; petroleum fractions, such as gasoline, kerosine andgas oil; and halides of these aromatic, aliphatic and alicyclichydrocarbons, particularly chlorides and bromides thereof. Alsoemployable are ethers such as ethyl ether and tetrahydrofuran. Of thesolvents, particularly preferable are aromatic hydrocarbons andaliphatic hydrocarbons.

[0346] In the benzene-insoluble organoaluminum oxy-compound for use inthe invention, the content of Al component which is soluble in benzeneat 60° C. is usually not more than 10%, preferably not more than 5%,particularly preferably not more than 2%, in terms of Al atom, and thebenzene-insoluble organoaluminum oxy-compound is insoluble or sparinglysoluble in benzene.

[0347] The organoaluminum oxy-compound employable in the invention is,for example, an organoaluminum oxy-compound containing boron andrepresented by the following formula (IV):

[0348] wherein R¹⁷ is a hydrocarbon group of 1 to 10 carbon atoms; andeach R¹⁸ may be the same or different and is a hydrogen atom, a halogenatom or a hydrocarbon group of 1 to 10 carbon atoms.

[0349] The organoaluminum compound containing boron and represented bythe formula (IV) can be prepared by causing an alkylboronic acidrepresented by the following formula (V) to react with an organoaluminumcompound in an inert solvent under an inert gas atmosphere at atemperature of −80° C. to room temperature for 1 minute to 24 hours.

R¹⁷—B—(OH)₂  (V)

[0350] wherein R¹⁷ is the same group as described above.

[0351] Examples of the alkylboronic acids represented by the formula (V)include methylboronic acid, ethylboronic acid, isopropylboronic acid,n-propylboronic acid, n-butylboronic acid, isobutylboronic acid,n-hexylboronic acid, cyclohexylboronic acid, phenyboronic acid,3,5-difluoroboronic acid, pentafluorophenylboronic acid and 3,5-bis(trifluoromethyl)phenylboronic acid. Of these, preferable aremethylboronic acid, n-butylboronic acid, isobutylboronic acid,3,5-difluorophenylboronic acid and pentafluorophenylboronic acid. Thealkylboronic acids are used singly or in combination of two or morekinds.

[0352] Examples of the organoaluminum compounds to be reacted with thealkylboronic acid include the same organoaluminum compounds as describedfor the organoaluminum compound (B-1a).

[0353] Of these, preferable are trialkylaluminums andtricycloalkylaluminums. Particularly preferable are trimethylaluminum,triethylaluminum and triisobutylaluminum. The organoaluminum compoundscan be used singly or in combination of two or more kinds.

[0354] The organoaluminum oxy-compounds (B-2) mentioned above are usedsingly or in combination of two or more kinds.

[0355] (B-3) Compound which Reacts with the Transition Metal Compound toform Ion pair

[0356] The compound (B-3) which reacts with the transition metalcompound to form an ion pair (referred to as “ionizing ionic compound”hereinafter), that is used in the invention, is a compound which reactswith the transition metal compound (A) to form an ion pair, and includesLewis acid, an ionic compound, a borane compound and a carboranecompound described in Japanese Patent Laid-Open Publications No.501950/1989, No. 502036/1989, No. 179005/1991, No. 179006/1991, No.207703/1991 and No. 207704/1991, and U.S. Pat. No. 5,321,106. Further,as ionizing ionic compound, heteropoly-compound or isopoly-compound maybe used.

[0357] The Lewis acid is, for example, a compound represented by BR₃ (Ris a phenyl group which may have a substituent such as fluorine, methylor trifluoromethyl, or a fluorine atom). Examples of such compoundsinclude trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron andtris(3,5-dimethylphenyl)boron.

[0358] The ionic compound is, for example, a compound represented by thefollowing formula (VI).

[0359] In the above formula, R¹⁹ is H⁺, carbonium cation, oxoniumcation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation,ferrocenium cation having a transition metal, or the like.

[0360] R²⁰ to R²³ may be the same or different, and are each an organicgroup, preferably an aryl group or a substituted aryl group.

[0361] Examples of the carbonium cations include tri-substitutedcations, such as triphenylcarbonium cation, tri(methylphenyl)carboniumcation and tri(dimethylphenyl)carbonium cation.

[0362] Examples of the ammonium cations include trialkylammoniumcations, such as trimethylammonium cation, triethylammonium cation,tripropylammonium cation and tributylammonium cation;N,N-dialkylanilinium cations, such as N,N-dimethylanilinium cation,N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation;and dialkylammonium cations, such as di(isopropyl)ammonium cation anddicyclohexylammonium cation.

[0363] Examples of the phosphonium cations include triarylphosphoniumcations, such as triphenylphosphonium cation,tri(methylphenyl)phosphonium cation and tri(dimethylphenyl)phosphoniumcation.

[0364] R¹⁹ is preferably carbonium cation or ammonium cation,particularly preferably triphenylcarbonium cation, N,N-dimethylaniliniumcation or N,N-diethylanilinium cation.

[0365] Also available as the ionic compound is a trialkyl-substitutedammonium salt, a N,N-dialkylanilinium salt, a dialkylammonium salt and atriarylphosphonium salt.

[0366] Examples of the trialkyl-substituted ammonium salts includetriethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron,tri(n-butyl) ammoniumtetra(phenyl)boron,trimethylarmmoniumtetra(p-tolyl)boron,trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron,tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniuntetra(m,m-dimethylphenyl)boron,tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron,tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron andtri(n-butyl)ammoniumtetra(o-tolyl)boron.

[0367] Examples of the N,N-dialkylanilinium salts includeN,N-dimethylaniliniumtetra(phenyl)boron,N,N-diethylaniliniumtetra(phenyl)boron andN,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron.

[0368] Examples of the dialkylammonium salts includedi(1-propyl)ammoniumtetra(pentafluorophenyl)boron anddicyclohexylammoniumtetra(phenyl)boron.

[0369] Further employable as the ionic compound istriphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,ferroceniumtetra(pentafluorophenyl)borate,triphenylcarbeniumpentaphenylcyclopentadienyl complex,N,N-diethylaniliniumpentaphenylcyclopentadienyl complex or a boroncompound represented by the following formula (VII) or (VIII).

[0370] wherein Et is an ethyl group.

[0371] Examples of the borane compounds include:

[0372] decaborane(14);

[0373] salts of anions, such as bis[tri(n-butyl)ammonium]nonaborate,bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate,bis[tri(n-butyl)ammonium]decachlorodecaborate andbis[tri(n-butyl)ammonium]dodecachlorododecaborate; and

[0374] salts of metallic borane anions, such astri(n-butyl)ammoniumbis(dodecahydridedodecaborate)cobaltate(II I) andbis[tri(n-butyl)ammonium]bis-(dodecahydridedodecaborate)nickelate(III).

[0375] Examples of the carborane compounds include:

[0376] salts of anions, such as 4-carbanonaborane(14),1,3-dicarbanonaborane(13), 6,9-dicarbadecaborane(14),dodecahydride-1-phenyl-1,3-dicarbanonaborane,dodecahydride-1-methyl-1,3-dicarbanonaborane,undecahydride-1,3-dimethyl-1,3-dicarbanonaborane,7,8-dicarbaundecaborane(13), 2,7-dicarbaundecaborane(13),undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,dodecahydride-11-methyl-2;7-dicarbaundecaborane,tri(n-butyl)ammonium-1-carbadecaborate,tri(n-butyl)ammonium-1-carbaundecaborate,tri(n-butyl)ammonium-1-carbadodecaborate,tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,tri(n-butyl)ammoniumbromo-1-carbadodecaborate,tri(n-butyl)ammonium-6-carbadecaborate(14),tri(n-butyl)ammonium-6-carbadecaborate(12),tri(n-butyl)ammonium-7-carbaundecaborate(13),tri(n-butyl)ammonium-7,8-dicarbaundecaborate(12),tri(n-butyl)ammonium-2,9-dicarbaundecaborate(12),tri(n-butyl)ammoniumdodecahydride-8-methyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydride-8-butyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydride-8-allyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydride-9-trimethylsilyl-7,8-dicarbaundecaborateand tri(n-butyl)ammoniumundecahydride-4,6-dibromo-7-carbaundecaborate;and

[0377] salts of metallic carborane anions, such astri(n-butyl)ammoniumbis(nonahydride-1,3-dicarbanonaborate)cobaltate(III),tri(n-butyl) ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)nickelate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cuprate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)aurate(III),tri(n-butyl)anmoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III),tri(n-butyl)ammoniumbis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III),tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate(III),bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate(IV),bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate(III)andbis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nickelate(IV).

[0378] The heteropoly-compounds comprise a heteroatom such as silicon,phosphorus, titanium, germanium, arsenic or tin, and at least onepolyatom selected from vanadium, niobium molybdenum and tungsten. Forexample, phosphovanadic acid, germanovanadic acid, arsenovanadic acid,phosphoniobic acid, germanoniobic acid, siliconomolybdic acid,phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid,arsenomolybdic acid, stannnomolybdic acid, phosphotungstic acid,germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid,phosphotungstovanadic acid, germanotungstovanadic acid,phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid,phosphomolybdotungstic acid and phosphomolybdoniobic acid, salts ofthese acid with a metal of Group 1 or 2 of the periodic table such aslithium, sodium, potassium, rubidium, cesium, beryllium, magnesium,calcium, strontium or barium, and further organic salts such astriphenylethyl salts of the above acids, as well as isopoly-compounds,but not limited thereto.

[0379] The heteropoly-compounds and isopoly-compounds mentioned abovemay be used singly or in combination of two or more kind.

[0380] The ionizing ionic compounds (B-3) mentioned above can be usedsingly or in combination of two or more kinds.

[0381] If the transition metal compounds according to the invention areused as catalyst in combination with the organoaluminum oxy-compound(B-2) such as methylaluminoxane as a cocatalyst, olefin compounds can bepolymerized with high polymerization activities. If the ionized ioniccompound (B-3) such as triphenylcarboniumtetrakis(pentafluorophenyl)borate is used as a cocatalyst, polyolefinshaving a very high molecular weight is produced with good activities.

[0382] In the olefin polymerization catalyst of the invention, thebelow-described carrier (C) can be used if necessary, in addition to theabove-mentioned transition metal compound (A) and at least one compound(B) selected from the organometallic compound (B-1), the organoaluminumoxy-compound (B-2) and the ionized ionic compound (B-3).

[0383] (C) Carrier

[0384] The carrier (C) for use in the invention is an inorganic ororganic compound in the form of granular or particulate solid. As theinorganic compound, porous oxide, inorganic chloride, clay, clay mineralor an ion-exchange layered compound is preferable.

[0385] Examples of the porous oxides include SiO₂, Al₂O₃, MgO, ZrO,TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂; and mixtures containing these oxides,such as SiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO2—Cr₂O₃ andSiO₂—TiO₂—MgO. Preferable are compounds each containing at least one ofSiO₂ and Al₂O₃ as the main component.

[0386] The inorganic oxides may contain a small amount of carbonate,sulfate, nitrate or oxide component, such as Na₂CO₃, K₂CO₃, CaCO₃,MgCO₃, Na₂SO₄, Al₂ (SO₄)₃, BaSO_(Mg(NO) ₃)₂, Al(NO₃)₃, Na₂O, K₂O orLi₂O.

[0387] Though the porous oxides differ in their properties depending onthe type and the preparation process thereof, the carrier preferablyused in the invention has a particle diameter of 10 to 300 μm,preferably 20 to 200 μm, a specific surface area of 50 to 1,000 m²/g,preferably 100 to 700 m²/g, and a pore volume of 0.3 to 3.0 cm³/g. Thecarrier can be used after calcined at 100 to 1,000° C., preferably 150to 700° C., if desired.

[0388] Examples of the inorganic chlorides employable in the inventioninclude MgCl₂, MgBr₂, MnCl₂ and MnBr₂. In the invention, the inorganicchloride may be used as it is, or can be used after pulverized by a ballmill, a vibration mill or the like. The inorganic chloride can be usedas fine particles of a precipitate obtained by dissolving the inorganicchloride in a solvent such as alcohol and then precipitating usingprecipitating agent.

[0389] The clay for use in the invention is generally constituted mainlyof clay mineral. The ion-exchange layered-compound is a compound havinga crystal structure wherein planes formed by ionic bonding or the likeare laminated in parallel to each other with a weak bond strength, andthe ions contained therein are exchangeable. Most of clay minerals areion-exchange layered compounds. As the clay, the clay minerals and theion-exchange layered compounds, not only natural ones but also syntheticones are employable.

[0390] Examples of such clay, clay minerals and ion-exchange layeredcompounds include clay, clay minerals and ion crystalline compoundshaving layered crystal structures such as hexagonal closest packingtype, antimony type, CdCl₂ type and CdI₂ type.

[0391] Particular examples of the clay and the clay minerals includekaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite,pyrophyllite, mica, montmorillonite, vermiculite, chlorite,palygorskite, kaolinite, nacrite, dickite and halloysite. Particularexamples of the ion-exchange layered compounds include crystalline acidsalts of polyvalent metals, such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂,α-Zr(KPO₄)₂.3H₂O, α-Ti(HPO₄)₂, α-Ti(HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O,γ-Zr(HPO₄)₂, γ-Ti(HPO₄)₂ and γ-Ti(NH₄PO₄)₂.H₂O.

[0392] As the clay, the clay minerals and the ion-exchange layeredcompounds, preferable are those having a pore volume, as measured onpores having a radius of not less than 20 Å by a mercury penetrationmethod, of not less than 0.1 cc/g, and particularly preferable are thosehaving a pore volume of 0.3 to 5 cc/g. The pore volume is measured onthe pores having a radius of 20 to 3×10⁴ Å by a mercury penetrationmethod using a mercury porosimeter. When a compound having a porevolume, as measured on pores having a radius of not less than 20 Å, ofless than 0.1 cc/g is used, high polymerization activities are apt to behardly obtained.

[0393] It is preferable that the clay and the clay minerals for use inthe invention are subjected to chemical treatments. A surface treatmentto remove impurities attached to the surface and a treatment having aninfluence on the crystal structure of the clay are both available.Examples of such treatments include acid treatment, alkali treatment,salt treatment and organic matter treatment. The acid treatmentcontributes to not only removing impurities from the surface but alsoeluting cations such as Al, Fe and Mg present in the crystal structureto thereby increase the surface area. The alkali treatment destroys thecrystal structure of clay to bring about change in the structure of theclay. The salt treatment and the organic matter treatment can produceionic complex, molecular complex or organic derivative to change thesurface area or the distance between layers.

[0394] In the ion-exchange layered compound for use in the invention,the exchangeable ions between layers can be exchanged with other largeand bulky ions utilizing ion exchange properties, whereby a layeredcompound having enlarged distance between layers can be obtained. Thatis, the bulky ion plays a pillar-like roll to support the layerstructure and is called a “pillar”. Introduction of other substancesbetween layers of a layered material is called “intercalation”.

[0395] Examples of the guest compounds to be intercalated includecationic inorganic compounds, such as TiCl₄ and ZrCl₄; metallicalcoholates, such as Ti(OR)₄, Zr(OR)₄, PO(OR)₃ and B(OR)₃ (R is ahydrocarbon group or the like); and metallic hydroxide ions, such as[Al₁₃O₄(OH)₂₄ ]⁷⁺, [Zr₄(OH)₁₄]²⁺and [Fe₃O(OCOCH₃)₆]⁺. These compoundscan be used singly or in combination of two or more kinds. Intercalationof these compounds can be carried out in the presence of polymersobtained by hydrolysis of metallic alcoholates such as Si(OR)₄, Al(OR)₃and Ge(OR)₄ (R is a hydrocarbon group or the like) or in the presence ofcolloidal inorganic compounds such as SiO₂. Examples of the pillarsinclude oxides produced by intercalation of the above-mentionedhydroxide ions between layers and then dehydration under heating.

[0396] The clay, clay minerals and the ion-exchange layered compoundsmentioned above may be used as they are, or may be used after subjectedto a treatment of ball milling, sieving or the like. Moreover, they maybe used after subjected to water adsorption or dehydration underheating. The clay, clay minerals and the ion-exchange layered compoundsmay be used singly or in combination of two or more kinds.

[0397] Of the above-mentioned materials, preferable are clay and clayminerals, and particularly preferable are montmorillonite, vermiculite,pectolite, teniolite and synthetic mica.

[0398] The organic compound is, for example, a granular or particulateorganic compound having a particle diameter of 10 to 300 μm. Examples ofsuch compounds include (co)polymers produced using, as main components,α-olefins of 2 to 14 carbon atoms such as ethylene, propylene, 1-buteneand 4-methyl-1-pentene, (co)polymers produced using, as a maincomponent, vinylcyclohexane or styrene, and modified products thereof.

[0399] In the olefin polymerization catalyst of the invention, thebelow-described specific organic compound (D) can be used if necessary,in addition to the transition metal compound (A), at least one compound(B) selected from the organometallic compound (B-1), the organoaluminumoxy-compound (B-2) and the ionized ionic compound (B-3), and the fineparticle carrier (C).

[0400] (D) Organic Compound Component The organic compound componentwhich can be used if necessary functions to improve polymerizability andproperties of the resulting polymers. Examples of the organic compoundsinclude alcohol, a phenolic compound, a carboxylic acid, a phosphoruscompound and sulfonate, but the organic compound employable in theinvention is not limited thereto.

[0401] The alcohol and the phenolic compound are represented by R³¹—OHwherein R³¹ is a hydrocarbon group of 1 to 50 carbon atoms or ahalogenated hydrocarbon group of 1 to 50 carbon atoms. The alcohol ispreferably a halogen atom-containing hydrocarbon. The phenolic compoundis preferably a phenolic compound wherein the α,α′-position of thehydroxyl group is substituted with a hydrocarbon group of 1 to 20 carbonatoms.

[0402] The carboxylic acid is represented by R³²—COOH wherein R³² is ahydrocarbon group of 1 to 50 carbon atoms or a halogenated hydrocarbongroup of 1 to 50 carbon atoms, preferably a halogenated hydrocarbongroup of 1 to 50 carbon atoms.

[0403] Preferred examples of the phosphorus compounds include phosphoricacids having P—O—H bond, phosphates having P—OR bond or P═O bond, andphosphine oxide compounds.

[0404] The sulfonate is represented by the following formula (IX):

[0405] wherein M is an atom of Group 1 to Group 14 of the periodictable; R³³ is a hydrocarbon group of 1 to 20 carbon atoms or ahalogenated hydrocarbon group of 1 to 20 carbon atoms; X is a hydrogenatom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or ahalogenated hydrocarbon group of 1 to 20 carbon atoms; m is an integerof 1 to 7; and n≦n≦7.

[0406]FIG. 1 shows steps for preparing the first olefin polymerizationcatalyst according to the invention.

[0407] In the polymerization, the components can be used in any way andin any order. Some examples of the processes are given below.

[0408] (1) The component (A) and at least one component (B) selectedfrom the organometallic compound (B-1), the organoaluminum oxy-compound(B-2) and the ionized ionic compound (B-3) (referred to simply as“component (B)” hereinafter) are fed to the polymerization reactor in anarbitrary order.

[0409] (2) A catalyst obtained by previously contacting the component(A) with the component (B) is fed to the polymerization reactor.

[0410] (3) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), and the component (B) are fed tothe polymerization reactor in an arbitrary order. In this case, thecomponents (B) may be the same or different.

[0411] (4) A catalyst component wherein the component (A) is supportedon the carrier (C), and the component (B) are fed to the polymerizationreactor in an arbitrary order.

[0412] (5) A catalyst component wherein the component (A) and thecomponent (B) are supported on the carrier (C) is fed to thepolymerization reactor.

[0413] (6) A catalyst component wherein the component (A) and thecomponent (B) are supported on the carrier (C), and the component (B)are fed to the polymerization reactor in an arbitrary order. In thiscase, the components (B) may be the same or different.

[0414] (7) A catalyst component wherein the component (B) is supportedon the carrier (C), and the component (A) are fed to the polymerizationreactor in an arbitrary order.

[0415] (8) A catalyst component wherein the component (B) is supportedon the carrier (C), the component (A) and the component (B) are fed tothe polymerization reactor in an arbitrary order. In this case, thecomponents (B) may be the same or different.

[0416] (9) A component wherein the component (A ) is supported on thecarrier (C) and a component wherein the component (B) is supported onthe carrier (C) are fed to the polymerization reactor in an arbitraryorder.

[0417] (10) A component wherein the component (A) is supported on thecarrier (C), a component wherein the component (B) is supported on thecomponent (C), and the component (B) are fed to the polymerizationreactor in an arbitrary order. In this case, the components (B) may bethe same or different.

[0418] (11) The component (A), the component (B) and the organiccompound component (D) are fed to the polymerization reactor in anarbitrary order.

[0419] (12) A component obtained by previously contacting the component(B) with the component (D), and the component (A) are fed to thepolymerization reactor in an arbitrary order.

[0420] (13) A component wherein the component (B) and the component (D)are supported on the carrier (C), and the component (A) are fed to thepolymerization reactor in an arbitrary order.

[0421] (14) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), and the component (D) are fed tothe polymerization reactor in an arbitrary order.

[0422] (15) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), the component (B) and thecomponent (D) are fed to the polymerization reactor in an arbitraryorder.

[0423] (16) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), and a component obtained bypreviously contacting the component (B) with the component (D) are fedto the polymerization reactor in an arbitrary order.

[0424] (17) A component wherein the component (A) is supported on thecarrier (C), the component (B) and the component (D) are fed to thepolymerization reactor in an arbitrary order.

[0425] (18) A component wherein the component (A) is supported on thecarrier (C) and a component obtained by contacting the component (B)with the component (D) are fed to the polymerization reactor in anarbitrary order.

[0426] (19) A catalyst component obtained by previously contacting thecomponent (A), the component (B) and the component (D) with each otheris fed to the polymerization reactor.

[0427] (20) A catalyst component which is obtained by previouslycontacting the component (A), the component (B) and the component (D)with each other, and the component (B) are fed to the polymerizationreactor in an arbitrary order. In this case, the components (B) may bethe same or different.

[0428] (21) A catalyst component wherein the component (A), thecomponent (B) and the component (D) are supported on the carrier (C) isfed to the polymerization reactor.

[0429] (22) A catalyst component wherein the component (A), thecomponent (B) and the component (D) are supported on the carrier (C),and the component (B) are fed to the polymerization reactor in anarbitrary order. In this case, the components (B) may be the same ordifferent.

[0430] An olefin may be prepolymerized onto the solid catalyst componentwherein the component (A) and the component (B) are supported on thecarrier (C).

[0431] In the process for olefin polymerization according to theinvention, an olefin is polymerized or copolymerized in the presence ofthe above-described olefin polymerization catalyst to obtain an olefinpolymer.

[0432] In the present invention, the polymerization can be carried outas any of liquid phase polymerization, such as solution polymerizationor suspension polymerization, and gas phase polymerization.

[0433] Examples of the inert hydrocarbon media used in the liquid phasepolymerization include aliphatic hydrocarbons, such as propane, butane,pentane, hexane, heptane octane, decane, dodecane and kerosine;alicyclic hydrocarbons, such as cyclopentane, cyclohexane andmethylcyclopentane; aromatic hydrocarbons, such as benzene, toluene andxylene; halogenated hydrocarbons, such as ethylene chloride,chlorobenzene and dichloromethane; and mixtures of these hydrocarbons.The olefin itself can be used as the solvent.

[0434] In the polymerization of an olefin using the olefinpolymerization catalyst, the component (A) is used in an amount ofusually 10⁻¹² to 10⁻² mol, preferably 10⁻¹⁰ to 10⁻³ mol, based on 1liter of the reaction volume. In the present invention, an olefin can bepolymerized with high polymerization activities, even if the component(A) is used in a relatively low concentration.

[0435] The component (B-1) is used in such an amount that the molarratio of the component (B-1) to the transition metal atom (M) in thecomponent (A) ((B-1)/(M)) becomes usually 0.01 to 100,000, preferably0.05 to 50,000. The component (B-2) is used in such an amount that themolar ratio of the aluminum atom in the component (B-2) to thetransition metal atom (M) in the component (A) ((B-2)/(M)) becomesusually 10 to 500,000, preferably 20 to 100,000. The component (B-3) isused in such an amount that the molar ratio of the component (B-3) tothe transition metal atom (M) in the component (A) ((B-3)/(M)) becomesusually 1 to 10, preferably 1 to 5.

[0436] The ratio of the component (D) to the component (B) is asfollows. When the component (B) is the component (B-1), the component(D) is used in such an amount that the (D)/(B-1) ratio by mol becomes0.01 to 10, preferably 0.1 to 5. When the component (B) is the component(B-2), the component (D) is used in such an amount that the molar ratioof the component (D) to the aluminum atom in the component (B-2)((D)/(B-2)) becomes 0.001 to 2, preferably 0.005 to 1. When thecomponent (B) is the component (B-3), the component (D) is used in suchan amount that the (D)/(B-3) ratio by mol becomes 0.01 to 10, preferably0.1 to 5.

[0437] The temperature for the olefin polymerization using the olefinpolymerization catalyst is in the range of usually −50 to 200° C.,preferably 0 to 170° C. The polymerization pressure is in the range ofusually atmospheric pressure to 100 kg/cm², preferably atmosphericpressure to 50 kg/cm². The polymerization reaction can be carried out byany of batchwise, semi-continuous and continuous processes. Thepolymerization can be conducted in two or more stages under differentreaction conditions.

[0438] The molecular weight of the resulting polymer can be adjusted byallowing hydrogen to exist in the polymerization system or by varyingthe polymerization temperature. Further, the molecular weight can beadjusted also by using the component (B) of different type.

[0439] Examples of the olefins which can be polymerized using the olefinpolymerization catalyst include:

[0440] straight-chain or branched α-olefins of 2 to 30, preferably 3 to20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene,3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene and 1-eicosene; and

[0441] cycloolefins of 3 to 30, preferably 3 to 20 carbon atoms, such ascyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,tetracyclododecene and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0442] Also employable are polar monomers. Examples of such monomersinclude α,β-unsaturated carboxylic acids, such as acrylic acid,methacrylic acid, fumaric acid, maleic anhydride, itaconic acid,itaconic anhydride and bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid;metallic salts of these acids, such as sodium salts, potassium salts,lithium salts, zinc salts, magnesium salts and calcium salts;α,β-unsaturated carboxylic esters, such as methyl acrylate, ethylacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methylmethacrylate, ethyl methacrylate, n-propyl methacrylate, isopropylmethacrylate, n-butyl methacrylate and isobutyl methacrylate; vinylesters, such as vinyl acetate, vinyl propionate, vinyl caproate, vinylcaprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate; andunsaturated glycidyl esters, such as glycidyl acrylate, glycidylmethacrylate and monoglycidyl itaconate. Furthermore, vinylcyclohexane,diene, polyene and the like are also employable. The diene and thepolyene are cyclic or chain compounds having 4 to 30, preferably 4 to 20carbon atoms and having two or more double bonds. Examples of suchcompounds include butadiene, isoprene, 4-methyl-1,3-pentadiene,1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene,1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norborneneand dicyclopentadiene;

[0443] 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene,5,9-dimethyl-1,4,8-decatriene; and further

[0444] aromatic vinyl compounds such as mono or poly alkylstyrenes(e.g., styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene andp-ethylstyrene),functional group-containing styrene derivatives (e.g.,methoxystyrene, ethoxystyrere, vinylbenzoic acid, methyl vinylbenzoate,vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyreneand divinylbenzene); and

[0445] 3-phenylpropyrene, 4-phenylpropyrene and α-methylstyrene.

[0446] The olefin polymerization catalyst of the invention exhibits highpolymerization activities, and by the use of the catalyst, polymers ofnarrow molecular weight distribution can be obtained. When two or morekinds of olefins are used, olefin copolymers of narrow compositiondistribution can be obtained.

[0447] The olefin polymerization catalyst of the invention can be usedalso for the copolymerization of an α-olefin and a conjugated diene.

[0448] Examples of the α-olefins used herein include the samestraight-chain or branched α-olefins of 2 to 30, preferably 2 to 20carbon atoms as described above. Of these, preferable are ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and1-octene. Particularly preferable are ethylene and propylene. Theseα-olefins can be used singly or in combination or two or more kinds.

[0449] Examples of the conjugated dienes include aliphatic conjugateddienes of 4 to 30, preferably 4 to 20 carbon atoms, such as1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene,1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene and1,3-octadiene. These conjugated dienes can be used singly or incombination of two or more kinds.

[0450] In the copolymerization of the α-olefin and the conjugated diene,non-conjugated diene or polyene is further employable, and examplesthereof include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene.

Second Olefin Polymerization Catalyst

[0451] The second olefin polymerization catalyst according to theinvention is formed from:

[0452] (A′) a transition metal compound represented by thebelow-described formula (II), and

[0453] (B) at least one compound selected from:

[0454] (B-1) an organometallic compound,

[0455] (B-2) an organoaluminum oxy-compound, and

[0456] (B-3) a compound which reacts with the transition metal compound(A′) to form an ion pair.

[0457] First, the components for forming the olefin polymerizationcatalyst of the invention are described.

[0458] (A′) Transition Metal Compound

[0459] The transition metal compound (A′) for use in the invention is atransition metal compound represented by the following formula (II):

[0460] wherein M is a transition metal atom of Group 3 to Group 11 ofthe periodic table,

[0461] R¹ to R¹⁰ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring,

[0462] n is a number satisfying a valence of M,

[0463] X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring,and

[0464] Y is a divalent bonding group containing at least one elementselected from the group consisting of oxygen, sulfur, carbon, nitrogen,phosphorus, silicon, selenium, tin and boron, and when it is ahydrocarbon group, the hydrocarbon group has 3 or more carbon atoms.

[0465] It is preferable that at least one of R⁶ and R¹⁰, especially bothof them, in the formula (II) is a halogen atom, a hydrocarbon group, aheterocyclic compound residue, an oxygen-containing group, anitrogen-containing group, a boron-containing group, a sulfur-containinggroup, a phosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group.

[0466] As M, R¹ to R¹⁰ and X in the formula (II), there can be used thesame groups as mentioned for M, R¹ to R⁶ and X in the formula (I),respectively. Specific examples of Y are described later on.

[0467] The transition metal compound represented by the formula (II) ispreferably a transition metal compound represented by the followingformula (II-a):

[0468] wherein M is a transition metal atom of Group 3 to Group 11,preferably Group 4 or 5, more preferably Group 4, of the periodic table,for example titanium, zirconium and halfnium, especially titanium.

[0469] R¹ to R¹⁰ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a hydrocarbon-substitutedsilyl group, an alkoxy group, an aryloxy group, an ester group, an amidogroup, an amino group, a sulfonamido group, a cyano group or a nitrogroup, and two or more of them may be bonded to each other to form aring,

[0470] n is a number satisfying a valence of M, usually an integer of 0to 4, preferably 1 to 4, more preferably 1 to 3.

[0471] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, an oxygen-containing group, a sulfur-containing groupor a silicon-containing group, and when n is 2 or greater, plural groupsmay be the same or different and may be bonded to each other to form aring.

[0472] Y is a divalent bonding group containing at least one elementselected from the group consisting of oxygen, sulfur, carbon, nitrogen,phosphorus, silicon, selenium, tin and boron, and when it is ahydrocarbon group, the hydrocarbon group has 3 or more carbon atoms.

[0473] The main chain of the bonding group Y has a structure comprisingpreferably 3 to 40, more preferably 4 to 10 atoms. The bonding group mayhave a substituent.

[0474] It is preferable that at least one of R⁶ and R¹⁰, preferably bothof them in the formula (II-a) is a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group,an ester group, an amido group, an amino group, a sulfonamido group, acyano group or a nitro group.

[0475] Specific examples of X and R¹ to R¹⁰ in the formula (II-a) arethe same as mentioned for X and R¹ to R⁶ in the formulae (I) and (I-a).X is particularly preferably a halogen atom, a hydrocarbon group of 1 to20 carbon atoms or a sulfinato group. When n is 2 or greater, pluralgroups X may be bonded to each other to form a ring such as an aromaticring or an aliphatic ring.

[0476] Specific examples of the divalent bonding groups includechalcogen atoms, such as —O—, —S— and —Se—; nitrogen—orphosphorus-containing groups, such as —NH—, —N(CH₃)—, —PH— and —P(CH₃)—;silicon atom-containing groups, such as —SiH₂— and —Si(CH₃)₂; tinatom-containing groups, such as —SnH₂— and —Sn(CH₃)₂; and boronatom-containing groups, such as —BH—, —B(CH₃) and —BF. Examples of thehydrocarbon groups include saturated hydrocarbon groups of 3 to 20carbon atoms, such as —(CH₂)₄—, —(CH₂)₅— and —(CH₂)₆—; cyclic saturatedhydrocarbon groups, such as cyclohexylidene and cyclohexylene; groupswherein these saturated hydrocarbon groups are partially substitutedwith 1 to 10 groups or atoms selected from hydrocarbon groups, halogenatoms (e.g., fluorine, chlorine and bromine) and hetero atoms (e.g.,oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin and boron);residual groups of cyclic hydrocarbons of 6 to 20 carbon atoms, such asbenzene, naphthalene and anthracene; residual groups of cyclic compoundscontaining hetero atoms and having 3 to 20 carbon atoms, such aspyridine, quinoline, thiophene and furan.

[0477] Examples of the transition metal compounds represented by theformula (II) are given below, but the transition metal compounds are notlimited to those examples.

[0478] In the above examples, Me is methyl, Ph is phenyl.

[0479] In the present invention, transition metal compounds whereintitanium is replaced with other metals than titanium, such as zirconiumor hafnium, in the above-exemplified compounds are also employable.

[0480] In the second olefin polymerization catalyst according to theinvention, the transition metal compound (A′) can be used in combinationwith other transition metal compounds, as for the aforesaid transitionmetal compound (A). Examples of the other transition metal compoundsinclude the aforesaid compounds (a-1) to (a-8).

[0481] In the second olefin polymerization catalyst according to theinvention, examples of the organometallic compounds (B-1), theorganoaluminum oxy-compounds (B-2) and the compounds which react withthe transition metal compound (A′) to form an ion pair include thosepreviously described.

[0482] In the second olefin polymerization catalyst according to theinvention, the aforesaid carrier (C) can be used if necessary, inaddition to the above-mentioned transition metal compound (A′) and atleast one compound (B) selected from the organometallic compound (B-1),the organoaluminum oxy-compound (B-2) and the ionized ionic compound(B-3), as in the first olefin polymerization catalyst. Further, theaforesaid specific organic compound (D) can also be used if necessary.

[0483]FIG. 2 shows steps for preparing the second olefin polymerizationcatalyst according to the invention.

[0484] The second olefin polymerization catalyst according to theinvention can be used for polymerizing the same olefins under the sameconditions as described for the first olefin polymerization catalyst.

Novel Transition Metal Compound

[0485] The novel transition metal compound according to the invention isrepresented by the following formula (III):

[0486] wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table,

[0487] m is an integer of 1 to 3,

[0488] R¹ is a hydrocarbon group, a hydrocarbon-substituted silyl group,a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an ester group, a thioestergroup, a sulfonester group or a hydroxyl group,

[0489] R² to R⁵ may be the same or different, and are each a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an ester group, a thioestergroup, an amido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group, a nitro group, acarboxyl group, a sulfo group, a mercapto group or a hydroxyl group,

[0490] R⁶ is a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, an ester group, a thioester group, an amido group, animido group, an imino group, a sulfonester group, a sulfonamido group ora cyano group,

[0491] two or more of R¹ to R⁶ may be bonded to each other to form aring,

[0492] when m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other,

[0493] n is a number satisfying a valence of M, and

[0494] X is a halogen atom, a hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group, aboron-containing group, an aluminum-containing group, aphosphorus-containing group, a halogen-containing group, a heterocycliccompound residue, a silicon-containing group, a germanium-containinggroup or a tin-containing group, and when n is 2 or greater, pluralgroups X may be the same or different and may be bonded to each other toform a ring.

[0495] As the transition metal compound of the formula (III), preferableis a transition metal compound represented by the following formula(III-a).

[0496] In the formula (III-a), M is a transition metal atom of Group 4or Group 5 of the periodic table, specifically titanium, zirconium,hafnium, vanadium, niobium or tantalum.

[0497] m is an integer of 1 to 3, preferably 2.

[0498] R¹ to R⁵ may be the same or different, and are each a hydrocarbongroup, an alkoxy group or a hydrocarbon-substituted silyl group.

[0499] R⁶ is a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, an alkylthio groupor a cyano group.

[0500] Two or more of R¹ to R⁶ may be bonded to each other to form aring.

[0501] When m is 2 or greater, two of the groups R¹ to R⁶ may be bondedto each other, with the proviso that the groups R¹ are not bonded toeach other.

[0502] n is a number satisfying a valence of M.

[0503] X is a halogen atom, a hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group,halogen-containing group or a silicon-containing group.

[0504] Preferable X is a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing, a sulfur-containing group or a silicon containinggroup.

[0505] When n is 2 or greater, plural groups X may be the same ordifferent and may be bonded to each other to form a ring.

[0506] Specific examples of R¹ to R⁶ and X include those described forthe above-mentioned formula (I).

[0507] Some examples of the novel transition metal compounds are givenbelow.

General Process for Preparing Transition Metal Compound

[0508] The transition metal compounds of the formulae (I), (II) and(III) can be prepared by any processes without specific limitation, forexample, in the manner as described below. First, the ligand composingthe transition metal compound can be obtained by reacting asalicylaldehyde compound with a primary amine compound of the formulaR¹—NH₂ (where R¹ has the meanings as described above), for example ananiline compound or an alkylamine compound. In more detail, bothstarting compounds are dissolved in a solvent, for example thosecommonly used in such reactions, preferably alcohols such as methanoland ethanol, and hydrocarbon solvents such as toluene. The resultingsolution is stirred for about 1 to 48 hours at room temperature to areflux temperature to obtain the corresponding ligand in a good yield.

[0509] In the preparation of ligands, catalysts for example acidcatalysts such as formic acid, acetic acid and toluenesulfonic acid canbe used. In order to proceed the reaction effectively, it is alsopossible to use dehydrating agents such as molecular sieves, magnesiumsulfate and sodium sulfate or to perform dehydration by the Dean Starkmethod.

[0510] The ligand thus obtained can then be reacted with a transitionmetal M-containing compound, to synthesize the desired transition metalcompound. Specifically, the ligand is dissolved in a solvent, and ifnecessary, is contacted with a base to prepare a phenoxide salt,followed by mixing with a metal compound such as a metallic halide or ametallic alkylate at a low temperature and stirring for about 1 to 48hours at −78° C. to room temperature or under reflux. Any solventsusually used in such reactions may be employed and preferable are polarsolvents such as ethers, e.g., tetrahydrofuran (THF) and hydrocarbonsolvents such as toluene. Examples of the bases which may be used forpreparing the phenoxide salt include, but not limited to metallic salts,such as lithium salts (e.g., n-butyllithium) and sodium salts (e.g.,sodium hydride) and organic bases such as triethylamine and pyridine.

[0511] Depending on the properties of the compound, the step ofpreparing the phenoxide salt may be omitted, and the ligand can bedirectly reacted with the metal compound to synthesize the correspondingtransition metal compound.

[0512] Further, it is possible that the transition metal M in thesynthesized compound is replaced with another transition metal byconventional methods. Furthermore, any one of R¹ to R⁶ which is H can besubstituted by a substituent other than H at any synthesis steps.

[0513] The novel transition metal compound represented by the formula(III), preferably the formula (III-a), can be favorably used as anolefin polymerization catalyst.

[0514] If the transition metal compound is used as an olefinpolymerization catalyst, (co)polymers of narrow molecular weightdistribution can be synthesized with high polymerization activities.

α-Olefin/conjugated Diene Copolymer

[0515] The α-olefin/conjugated diene copolymer according to theinvention comprises 1 to 99.9% by mol of constituent units derived froman α-olefin and 99 to 0.1% by mol of constituent units derived from aconjugated diene, and preferably comprises 50 to 99.9% by mol ofconstituent units derived from an α-olefin and 50 to 0.1% by mol ofconstituent units derived from a conjugated diene.

[0516] Examples of the α-olefins include the same straight-chain orbranched α-olefins of 2 to 30, preferably 2 to 20 carbon atoms asdescribed above. Of these, preferable are ethylene, propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Particularlypreferable are ethylene and propylene. These α-olefins can be usedsingly or in combination or two or more kinds.

[0517] Examples of the conjugated dienes include aliphatic conjugateddienes of 4 to 30, preferably 4 to 20, preferably 4 to 20 carbon atoms,such as 1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene,1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene and1,3-octadiene. These conjugated dienes can be used singly or incombination of two or more kinds.

[0518] In the copolymerization of the α-olefin and the conjugated diene,non-conjugated diene or polyene is further employable, and examplesthereof include 1,4-pentadiene, 1,5-hexadiene:, 1,4-hexadiene,1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene.

[0519] In the polymer chain of the α-olefin/conjugated diene copolymerof the invention, the content of 1,2-cyclopentane skeleton derived fromthe conjugated diene is not more than 1% by mol, preferably such acontent that the 1,2-cyclopentadiene skeleton can be regarded to besubstantially not contained (i.e., less than 0.1% by mol). When thecontent of the 1,2-cyclopentane skeleton is less than 0.1% by mol, thecontent is regarded to be lower than the detection limit and is notintroduced into the calculation of all the conjugated diene units.

[0520] In the polymer chain of the α-olefin/conjugated diene copolymerof the invention, the proportion of the 1,2-cyclopentane skeleton to allthe diene units is not more than 20%, preferably not more than 10%. Theproportions of other insertions of the dienes (e.g., 1,4-cis, 1,4-trans,1,2-vinyl) in the α-olefin/conjugated diene copolymer are arbitrary. Theproportions can be determined by ¹³C-NMR and ¹H-NMR in accordance withthe method described in “Die Makromolekulare Chemie”, volume 192, p.2591 (1991).

[0521] The α-olefin/conjugated diene copolymer has a molecular weightdistribution (Mw/Mn) of not more than 3.5 and has a uniform compositiondistribution. The weight average molecular weight (Mw) of the copolymeris not less than 1,000, preferably not less than 5,000.

[0522] Since the α-olefin/conjugated diene copolymer has double bonds inits main chain or side chain, it can be variously modified. For example,by virtue of modification with a peroxide, the double bonds can beepoxidized to introduce epoxy groups of high reactivity into thecopolymer. Such a modification makes the copolymer possible to be usedas a thermoplastic resin or a reactive resin. The double bonds can alsobe utilized in the Diels-Alder reaction or the Michael additionreaction. Further, in case of the copolymer having double bonds in themain chain, the copolymer can be improved in heat resistance and ozoneresistance by selectively hydrogenating the double bonds to saturatethem.

[0523] The α-olefin/conjugated diene copolymer of the invention may bemodified partially or fully with an unsaturated carboxylic acid, itsderivative or an aromatic vinyl compound, and the degree of modificationis preferably in the range of 0.01 to 30% by weight.

[0524] The monomer used for the modification (referred to as “graftmonomer” hereinafter) is, for example, an unsaturated carboxylic acid,its derivative or an aromatic vinyl compound. Examples of theunsaturated carboxylic acids include acrylic acid, methacrylic acid,maleic acid, fumaric acid and itaconic acid. Examples of the derivativesof unsaturated carboxylic acids include acid anhydrides, esters, amides,imides and metallic salts thereof, such as maleic anhydride, citraconicanhydride, itaconic anhydride, methyl acrylate, methyl methacrylate,ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethylmaleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate,diethyl itaconate, acrylamide, methacrylamide, maleic acid monoamide,maleic acid diamide, maleic acid-N-monoethylamide, maleicacid-N,N-diethylamide, maleic ac-d-N-monobutylamide, maleicacid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide,fumaric acid-N-monoethylamide, fumaric acid-N,N-diethylamide, fumaricacid-N-monobutylamide, fumaric acid-N,N-dibutylamide, maleimide,N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodiummethacrylate, potassium acrylate and potassium methacrylate. Of thegraft monomers, maleic anhydride is preferably employed.

[0525] Examples of the aromatic vinyl compounds include: styrene;

[0526] mono or polyalkylstyrenes, such as o-methylstyrene,m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene,m-ethylstyrene and p-ethylstyrene;

[0527] functional group-containing styrene derivatives, such asmethoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate,vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyreneand divinylbenzene; and

[0528] others, such as 3-phenylpropylene, 4-phenylbutene anda-methylstyrene. Of these, styrene or 4-methoxystyrene is preferable

[0529] For graft copolymerizing the α-olefin/conjugated diene copolymerwith the graft monomer to prepare a modified copolymer, various knownprocesses are available.

[0530] For example, the α-olefin/conjugated diene copolymer and thegraft monomer are heated at a high temperature in the presence orabsence of a solvent and in the presence or absence of a radicalinitiator to perform graft copolymerization. In the reaction, the graftmonomers may be used in combination.

[0531] In order to prepare a partially or wholly graft-modifiedα-olefin/conjugated diene copolymer having a graft ratio of 0.01 to 30%by weight, it is preferable from the viewpoint of industrial productionthat a graft-modified α-olefin/conjugated diene copolymer having a highgraft ratio is prepared and the thus graft-modified copolymer is thenmixed with an unmodified α-olefin/conjugated diene copolymer to adjustthe graft ratio, because the concentration of the graft monomer in thecomposition can be adjusted as desired. It is also possible that a givenamount of a graft monomer is blended with the α-olefin/conjugated dienecopolymer from the first to perform graft modification.

[0532] Referring to the degree of modification of theα-olefin/conjugated diene copolymer with the graft monomer, the graftratio to the whole resin composition is in the range of preferably 0.01to 30% by weight, particularly preferably 0.05 to 10% by weight.

[0533] The α-olefin/conjugated diene copolymer of the invention(including the above-mentioned modified product) may be blended with (i)a polyolefin resin and optionally, with (ii) a filler to form resincompositions useful for various applications

[0534] (i) Polyolefin Resin

[0535] The polyolefin resin (i) which may be blended with theα-olefin/conjugated diene copolymer of the invention may be any of acrystalline polyolefin and an amorphous polyolefin, or may be a mixtureof thse polyolefin resins.

[0536] The crystalline polyolefin is, for example, a homopolymer or acopolymer of an α-olefin of 2 to 20 carbon atoms or a cycloolefin. Theamorphous polyolefin is, for example, a copolymer of one or moreα-olefins of 2 to 20 carbon atoms and one or more cycloolefins.

[0537] Examples of the α-olefins of 2 to 20 carbon atoms includeethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene,4,4-dimethyl-1-hexene, 1-octene, 3-methyl-1-butene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and1-eicosene.

[0538] Examples of the cycloolefins include cyclopentene, cycloheptene,cyclohexene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene and2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0539] Examples of the crystalline polyolefin resins include thefollowing (co)polymers (1) to (11). Of the copolymers, particularlypreferable are the copolymers (3) and (5).

[0540] (1) Ethylene homopolymer (produced by any of low-pressure andhigh-pressure processes)

[0541] (2) Copolymer of ethylene and not more than 20% by mol of anotherα-olefin, vinyl monomer (e.g., vinyl acetate, ethyl acrylate) orcycloolefin

[0542] (3) Propylene homopolymer

[0543] (4) Random copolymer of propylene and not more than 20% by mol ofanother α-olefin

[0544] (5) Block copolymer of propylene and not more than 30% by mol ofanother α-olefin

[0545] (6) 1-Butene homopolymer

[0546] (7) Random copolymer of 1-butene and not more than 20% by mol ofanother α-olefin

[0547] (8) 4-Methyl-1-pentene homopolymer

[0548] (9) Random copolymer of 4-methyl-1-pentene and not more than 20%by mol of another α-olefin

[0549] (10) Cyclopentene homopolymer

[0550] (11) Random copolymer of cyclopentene and not more than 20% bymol of another α-olefin

[0551] As the “another α-olefin” in the above (co)polymers (1) to (11),ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octenefrom among the aforesaid examples is preferably employed. As thecycloolefin, cyclopentene, cyclohexene, norbornene or tetracyclododeceneis preferably employed.

[0552] The crystalline polyolefin resin desirably has a melt flow rate(measured at 230° C. under a load of 2.16 kg in accordance with ASTMD1238-65T) of 0.01 to 100 g/10 min, preferably 0.3 to 70 g/10 min, and acrystallinity, as measured by X-ray diffractometry, of usually 5 to100%, preferably 20 to 80%.

[0553] The crystalline polyolefin resin can be prepared by aconventional process.

[0554] Examples of the amorphous polyolefin resins include the following(co)polymers.

[0555] (1) Norbornene homopolymer

[0556] (2) Copolymer of ethylene and norbornene, or copolymer ofethylene, norbornene and another α-olefin

[0557] (3) Copolymer of ethylene and tetracyclododecene, or copolymer ofethylene, tetracyclododecene and another α-olefin

[0558] (ii) Filler

[0559] As the fillers (ii), which may be blended with theα-olefin/conjugated diene copolymer of the invention, those generallyused can be used without specific limitation.

[0560] Examples of the inorganic fillers include:

[0561] powdered fillers, such as silicates (e.g., powdered talc,kaolinite, calcined clay, pyrophillite, sericite, wollastonite),carbonates (precipitated calcium carbonate, heavy calcium carbonate,magnesium carbonate), hydroxides (e.g., aluminum hydroxide, magnesiumhydroxide), oxides (e.g., zinc oxide, zinc white, magnesium oxide), andsynthetic silicic acids or silicates (e.g., hydrated calcium silicate,hydrated aluminum silicate, hydrated silicic acid, silicic anhydride);

[0562] flaky fillers, such as mica;

[0563] fibrous fillers, such as basic magnesium sulfate whisker, calciumtitanate whisker, aluminum borate whisker, sepiolite, PMF (processedmineral fiber), xonotlite, potassium titanate and ellestadite; and

[0564] balloon fillers, such as glass balloon and fly ash balloon.

[0565] These fillers can be used singly or in combination of two or morekinds.

[0566] When the α-olefin/conjugated diene copolymer is blended with thepolyolefin resin (i) and the filler (ii), the α-olefin/conjugated dienecopolymer is desirably contained in an amount of 10 to 90 parts byweight, preferably 15 to 80 parts by weight, more preferably 20 to 75parts by weight, based on 100 parts by weight of the total of theα-olefin/conjugated diene copolymer, the polyolefin resin (i) and thefiller (ii).

[0567] If the content of the α-olefin/conjugated diene copolymer is usedin this amount, the α-olefin/conjugated diene copolymer composition hasexcellent moldability and is capable of providing molded products havingnot only excellent impact resistance, weathering resistance and heatstability but also excellent rigidity, strength and heat resistance.

[0568] The polyolefin resin (i) is contained in an amount of 1 to 99parts by weight, preferably 10 to 85 parts by weight, more preferably 10to 85 parts by weight, based on 100 parts by weight of the total of theresulting composition.

[0569] If the polyolefin resin (i) is used in this amount, thecomposition having not only excellent impact resistance and coldresistance but also excellent rigidity, strength, heat resistance andmoldability can be obtained.

[0570] The filler (ii) is contained in an amount of 0 to 40 parts byweight, preferably 0 to 30 parts by weight, based on 100 parts by weightof the total of the resulting composition. If the filler (ii) iscontained in this amount, the composition having excellent rigidity,surface appearance and heat resistance can be obtained.

[0571] Further, to the α-olefin/conjugated diene copolymer composition,various additives, such as nucleating agents, antioxidants, hydrochloricacid absorbers, heat stabilizers, light stabilizers, ultraviolet lightabsorbers, lubricants, antistatic agensts, flame retardants, pigments,dyes, dispersants, copper harm inhibitors, neutralizing agents, foamingagents, plasticizers, anti-foaming agents, crosslinking agents,crosslinking aids, crosslinking accelerators, flow property improvers(e.g., peroxide), weld strength improvers, processing aids, weatheringstabilizers and blooming inhibitors, may be added in an amount notdetrimental to the objects of the invention. These optional additivesmay be used in combination of two or more kinds.

Effect of the Invention

[0572] The olefin polymerization catalyst according to the inventionexhibits high polymerization activities on olefins.

[0573] In the process for olefin polymerization according to theinvention, an olefin (co)polymer of narrow molecular distribution can beproduced with high polymerization activities. When an α-olefin and aconjugated diene are copolymerized, a copolymer containing almost no1,2-cyclopentane skeleton in the polymer chain can be produced.

[0574] The novel transition metal compound according to the invention isuseful for an olefin polymerization catalyst, and provides an olefin(co)polymer of narrow molecular weight distribution with highpolymerization activities.

[0575] The α-olefin/conjugated diene copolymer according to theinvention has a narrow molecular weight distribution and contains almostno cyclopentane skeleton in the polymer chain.

EXAMPLE

[0576] The present invention is further described with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

[0577] Structures of the compounds obtained by Synthesis Examples weredetermined by 270 MHz ¹H-NMR (GSH-270 of Japan Electron OpticsLaboratory Co., Ltd.), FT-IR (SHIMAZU FTIR-82OOD), FD-mass spectrometry(SX-102A of Japan Electron Optics Laboratory Co., Ltd.), metal contentanalysis (SHIMAZU ICPS-8000, ICP method after dry ashing and dilutenitric acid dissolution), and carbon, hydrogen and nitrogen contentanalysis (CHNO type of Helaus Co.).

[0578] Structures of the compounds A-1 and B-1 were further decided byX-ray crystal structure analysis. The measurement was made by effectingMo—K a-ray irradiation using a Rigaku AFC7R four-axis diffractometer.The structure analysis was made by a direct method (SIR92), and thestructure optimization was made in accordance with TeXan crystalstructure analysis program.

[0579] Further, the intrinsic viscosity [η] was measured indecahydronaphthalene at 135° C. The molecular weight distribution(Mw/Mn) was measured by the gas permeation chromatography (GPC) usingo-dichlorobenzene as a solvent at 140° C.

[0580] Specific syntheses of ligands are given below.

Ligand Synthesis Example 1

[0581] Synthesis of Ligand (L1)

[0582] To a 100 ml reactor thoroughly purged with nitrogen, 40 ml ofethanol, 0.71 g (7.62 mmol) of aniline and 1.35 g (7.58 mmol) of3-t-butylsalicylaldehyde were introduced, and they were stirred at roomtemperature for 24 hours. The reaction solution was concentrated underreduced pressure to remove the solvent. Then, 40 ml of ethanol was addedagain, and the mixture was stirred at room temperature for 12 hours. Thereaction solution was concentrated under reduced pressure to obtain 1.83g (7.23 mmol, yield: 95%) of a compound represented by the followingformula (L1) as an orange oil.

[0583]¹H-NMR (CDCl₃): 1.47 (s, 9H), 6.88 (dd, 1H), 7.24-7.31 (m, 4H),7.38-7.46 (m, 3H), 8.64 (s, 1H), 13.95 (s, 1H) IR (neat): 1575, 1590,1610 cm⁻¹ FD-mass spectrometry: 253

Ligand Synthesis Example 2

[0584] Synthesis of Ligand (L2)

[0585] To a 100 ml reactor thoroughly purged with nitrogen, 30 ml ofethanol, 1.34 g (9.99 mmol) of a-naphthylamine and 1.40 g (7.86 mmol) of3-t-butylsalicylaldehyde were introduced. After addition of 5 g ofmolecular sieves 3A, the mixture was stirred under reflux for 8 hoursand then at room temperature for 12 hours. The reaction solution wasconcentrated under reduced pressure and the residue was purified using asilica gel column to obtain 2.35 g (7.75 mmol, 98% yield) of a compoundas an orange oil represented by the following formula (L2).

[0586]¹H-NMR (CDCl3): 1.50 (s, 9H), 6.90-7.90 (m, 11H), 8.30-8.50 (m,1H), 13.90 (s, 1H) FD-mass spectrometry: 303

Ligand Synthesis Example 3

[0587] Synthesis of Ligand (L3)

[0588] To a 100 ml reactor thoroughly purged with nitrogen, 30 ml ofethanol, 0.90 g (12-0 mmol) of t-butylamine and 1.78 g (10.0 mmol) of3-t-butylsalicylaldehyde were introduced. After addition of 5 g ofmolecular sieves 3A, the mixture was stirred at room temperature for 12hours. The reaction solution was concentrated under reduced pressure andthe residue was purified using a silica gel column to obtain 2.17 g (9.3mmol, 93% yield) of a compound as an fluorescent yellow oil representedby the following formula (L3).

[0589]¹H-NMR (CDCl₃): 1.20 (s, 9H), 1.42 (s, 9H), 6.50-7.50 (m, 3H),8.38 (s, 1H), 13.80 (s, 1H) FD-mass spectrometry: 233

Ligand Synthesis Examples 4-42

[0590] Ligands L4 to L42 were synthesized in the similar manner as inthe forgoing Ligand Synthesis Examples.

[0591] The identification of their structures were made by ¹H-NMR andFD-mass spectrometry.

[0592] Specific syntheses of transition metal compounds according to thepresent invention are given below.

[0593] Synthesis of Compound A-1

[0594] To a 300 ml reactor thoroughly dried and purged with argon, 1.785g (7.05 mmol) of compound L1 and 100 ml of diethyl ether wereintroduced, and they were cooled to −78° C. and stirred. After 4.78 mlof n-butyllithium (1.55 mmol/ml n-hexane solution, 7.40 mmol) wasdropwise added over a period of 5 minutes, the temperature was slowlyraised to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasslowly dropwise added to a mixture of 7.05 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 3.53 mmol) and 40ml of diethyl ether which had been been cooled to −78° C.

[0595] After the dropwise addition was completed, the temperature wasslowly raised to room temperature with stirring. After stirring foranother 8 hours at room temperature, the reaction solution was filteredwith a glass filter, and the resulting solid was dissolved and washedwith 50 ml of methylene chloride to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 10 ml of methylene chloride. To the solution was thenslowly added 70 ml of pentane with stirring. The mixture was allowed tostand at room temperature to precipitate red brown crystals. Thecrystals were separated by filtration with a glass filter, washed withpentane and then vacuum dried to obtain 1.34 g (2.15 mmol, yield: 61%)of compound A-1 represented by the following formula as red browncrystals.

[0596] Compound A-1

[0597]¹H-NMR (CDCl₃): 1.35 (s, 18H), 6.82-7.43 (m, 16H), 8.07 (s, 2H) IR(KBr): 1550, 1590, 1600 cm⁻¹ FD-mass spectrometry: 622 (M+) Elementalanalysis:

[0598] Ti: 7.7% (7.7)

[0599] C: 65.8% (65.5), H: 6.0% (5.8), N: 4.5% (4.5) Calculated valuesin pharentheses. Melting point: 265° C. X-ray crystal structureanalysis: The structure of compound A-1 is shown in FIG. 3.

Synthesis Example 2

[0600] Synthesis of Compound B-1

[0601] To a 200 ml reactor thoroughly dried and purged with argon, 1.53g (6.04 mmol) of compound L1 and 60 ml of tetrahydrofuran wereintroduced, and they were cooled to −78° C and stirred. After 4.1 ml ofn-butyllithium (1.55 mmol/ml n-hexane solution, 6.34 mmol) was dropwiseadded over a period of 5 minutes, the temperature was slowly raised toroom temperature, and stirring was continued at room temperature for 4hours. To the reaction solution was added 10 ml of tetrahydrofuran, andthe mixture was slowly added to a solution of 0.70 g of zirconiumtetrachloride (purity: 99.9%, 3.02 mmol) in 30 ml of tetrahydrofuranwhich had been cooled to −78° C. After the addition, the temperature wasslowly raised to room temperature. The reaction solution was stirred for2 hours at room temperature and then further stirred for another 4 hoursunder reflux.

[0602] The reaction solution was concentrated under reduced pressure,and the solid precipitated was washed with 50 ml of methylene chlorideand filtered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 30 ml of diethyl ether. The solution was allowed to standfor one day at −20° C. in a nitrogen atmosphere to precipitate yellowcrystals. The solid was separated by filtration, washed with hexane andthen vacuum dried to obtain 1.09 g (1.63 mmol, yield: 54%) of compoundB-1 represented by the following formula as fluorescent yellow crystals.

[0603]¹H—NM (CDCl₃): 1.33 (s, 18H), 6.78-7.42 (m, 16H), 8.12 (2H) IR(KBr): 1550, 1590, 1605 cm⁻¹ FD-mass spectrometry: 664 (M+) Elementalanalysis:

[0604] Zr: 13.5% (13.7)

[0605] C: 61.0% (61.2), H: 5.5% (5.4), N: 4.2% (4.2) Calculated valuesin pharentheses. Melting point: 287° C. X-ray crystal structureanalysis: The structure of compound B-1 is shown in FIG. 4.

Synthesis Example 3

[0606] Synthesis of Compound C-1

[0607] To a 100 ml reactor thoroughly dried and purged with argon, 0.66g (2.60 mmol) of compound (L1) and 8 ml of diethyl ether wereintroduced, and they were cooled to −78° C. and stirred. After 1.81 mlof n-butyllithium (1.55 mmol/ml n-hexane solution, 2.80 mmol) wasdropwise added over a period of 5 minutes, the temperature was slowlyraised to room temperature, and stirring was continued at roomtemperature for 2 hours. To the reaction solution was added 10 ml oftetrahydrofuran, and the mixture was slowly added to a solution of 0.385g of hafnium tetrachloride (purity: 99.9%, 3.02 mmol) in 10 ml oftetrahydrofuran which had been cooled to −78° C. After the addition, thetemperature was slowly raised to room temperature. The reaction solutionwas stirred for 2 hours at room temperature and then further stirred foranother 2 hours under heating at 50° C.

[0608] The reaction solution was concentrated under reduced pressure,and the solid precipitated was washed with 20 ml of methylene chlorideand filtered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasreslurried in 10 ml of diethyl ether at room temperature for 1 hour andseparated by filtration. The solid was washed with hexane and thenvacuum dried to obtain 0.33 g (0.40 mmol, yield: 33%) of compound C-1represented by the following formula as fluorescent yellow whitecrystals.

[0609]¹H-NMR (CDCl₃): 1.30 (s, 18H), 6.70-7.50 (m, 16H), 3.18 (s, 2H)FD-mass spectrometry: 754 (M+) Elemental analysis:

[0610] Hf: 23.5% (23.7)

[0611] C: 54.4% (54.2), H: 4.8% (4.8), N: 3.6% (3.7) Calculated valuesin pharentheses. Melting point: 277° C.

Synthesis Example 4

[0612] Synthesis of Compound D-1

[0613] To a 100 ml reactor thoroughly dried and purged with argon, 0.61g (2.40 mmol) of compound (L1) and 10 ml of diethyl ether wereintroduced, and they were cooled to −78° C. and stirred. After 1.61 mlof n-butyllithium (1.55 mmol/ml n-hexane solution, 2.50 mmol) wasdropwise added over a period of 5 minutes, the temperature was slowlyraised to room temperature, and stirring was continued at roomtemperature for 4 hours. The reaction solution was slowly added to asolution of 0.385 g of hafnium tetrachloride (purity: 99.9%, 3.02 mmol)in 10 ml of diethyl ether which had been cooled to −78° C. After theaddition, the temperature was slowly raised to room temperature, and thereaction solution was stirred for 4 hours at room temperature.

[0614] The reaction solution was concentrated under reduced pressure,and the solid precipitated was washed with 20 ml of methylene chlorideand filtered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 1 ml of diethyl ether. To the solution was slowly added 10ml of hexane with stirring to precipitate black green solid. The solidwas separated by filtration, reslurried and washed with hexane at roomtemperature for 1 hour and then vacuum dried to obtain 0.55 g (0.88mmol, yield: 73%) of compound D-1 represented by the following formulaas a blue black powder.

[0615]¹H-NMR (CDCl₃): unmeasurable because of paramagnetic metalcomplex. FD-mass spectrometry: 625 (M+) Elemental analysis:

[0616] V: 8.4%(3.1)

[0617] C: 65.3%(65-2), H: 5.5% (5.3), N: 4.5%(4.8) Calculated values inpharentheses.

Synthesis Example 5

[0618] Synthesis of Compound E-1

[0619] To a 100 ml reactor thoroughly dried and purged with argon, 0.61g (2.40 mmol) of compound (L1) and 10 ml of diethyl ether wereintroduced, and they were cooled to −78° C. and stirred. After 1.60 mlof n-butyllithium (1.55 mmol/ml n-hexane solution, 2.50 mmol) wasdropwise added over a period of 5 minutes, the temperature was slowlyraised to room temperature, and stirring was continued at roomtemperature for 4 hours. To the reaction solution was added 5 ml oftetrahydrofuran, and the mixture was slowly added to a solution of 0.34g of niobium pentachloride (purity: 95%, 1.20 mmol) in 10 ml oftetrahydrofuran which had been cooled to −78° C. After the addition, thetemperature was slowly raised to room temperature, and the reactionsolution was stirred at room temperature for 15 hours.

[0620] The reaction solution was concentrated under reduced pressure,and the solid precipitated was washed with 20 ml of methylene chlorideand filtered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 3 ml of diethyl ether. To the solution was slowly dropwiseadded 12 ml of hexane at room temperature with stirring to precipitateblack solid. The solid was separated by filtration, reslurried andwashed with hexane at room temperature for 1 hour and then vacuum driedto obtain 0.36 g (0.51 mmol, yield: 43%) of fluorescent yellow whitecompound E-1 represented by the following formula.

[0621]¹H-NMR (CDCl₃): 1.46 (s, 18H), 7.20-7.50 (m, 16H), 8.65 (s, 2H)FD-mass spectrometry: 702 (M+) Elemental analysis:

[0622] Nb: 13.0% (13.2)

[0623] C: 58.4% (53.0), H: 5.0% (5.2), N: 3.9% (4.0) Calculated valuesin pharenthesis

Synthesis Example 6

[0624] Synthesis of Compound F-1

[0625] To a 100 ml reactor thoroughly dried and purged with argon, 0.61g (2.40 mmol) of compound (L1) and 10 ml of toluene were introduced, andthey were cooled to −40° C. and stirred. To the mixture, 0.43 g of solidtantalum pentachloride (purity: 99.99%, 1.20 mmol) was slowly added.After the addition, the temperature was slowly raised to roomtemperature, then further raised to 60° C., and stirring was continuedfor 16 hours.

[0626] To the reaction solution was added 30 ml of methylene chloride,and the insolubles were filtered. The filtrate was concentrated underreduced pressure, and to the concentrate was added 8 ml of hexane toseparate out an orange viscous oil. The oil portion was separated anddissolved in 1 ml of diethyl ether. To the solution was slowly dropwiseadded 9 ml of hexane with stirring to precipitate bright yellow solid.The solid was separated by filtration, reslurried and washed hexane atroom temperature for 1 hour and then vacuum dried to obtain 0.15 g (0.26mmol, yield: 22%) of compound F-1 represented by the following formulaas a bright yellow powder.

[0627]¹H-NMR (CDCl₃): 1.50 (s, 9H), 6.80-7.75 (m, 8H), 8.23 (s, 1H)FD-mass spectrometry: 575 (M+) Elemental analysis:

[0628] Ta: 31.0% (31.5)

[0629] C: 58.4% (58.0), H: 3.3% (3.2), N: 4.5% (4.8) Calculated valuesin pharentheses.

Synthesis Example 7

[0630] Synthesis of Compound A-2

[0631] After charging 0.91 g (3.0 mmol) of compound L2 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.90 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.3 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was cooledto −78° C. and then slowly added dropwise to a mixture of 3.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.50mmol) and 10 ml of diethyl ether. After completion of the dropwiseaddition, stirring was continued while slowly increasing the temperatureto room temperature. After further stirring for 8 hours at roomtemperature, the reaction solution was filtered with a glass filter. Theresulting solid was dissolved and washed in 50 ml of methylene chloride,and the insoluble portion was removed by filtration. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with diethyl ether and hexane and dried under reducedpressure to obtain 0.53 g (0.73 mmol, 49% yield) of compound A-2 as darkbrown crystals represented by the formula given below.

[0632]¹H-NMR(CDCl₃): 0.86 (s,18H), 6.85-7.05 (m,6H), 7.15-7.30 (m,4H),7.35-7.90 (m, 10H), 8.45 (s,2H) FD-mass spectrometry: 722 (M+) Elementalanalysis: Ti: 6.6% (6.6) C: 69.9% (69.7), H: 5.5% (5.6), N: 3.4% (3.9)Calculated values in parentheses.

Synthesis Example 8

[0633] Synthesis of Compound B-2

[0634] After charging 0.91 g (3.0 mmol) of compound L2 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.94 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.0 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was thenslowly added dropwise to a 10 ml tetrahydrofuran solution containingzirconium tetrachloride (0.35 g, 1.50 mmol) which had been cooled to−78° C. After completion of the dropwise addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 8 hours at room temperature, the reactionsolution was concentrated to dryness, the residue was dissolved andwashed in 50 ml of methylene chloride, and then the insoluble portionwas removed by filtration. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.21 g (0.73 mmol,18% yield) of compound B-2 as yellow crystals represented by the formulagiven below.

[0635]¹H-NMR(CDCl₃): 1.11-1.70 (m,18H), 6,80-8.30 (m,20H), 8.33-8.48(m,2H) FD-mass spectrometry: 766 (M+) Elemental analysis: Zr: 12.1%(11.9) Calculated value in parentheses.

Synthesis Example 9

[0636] Synthesis of Compound A-3

[0637] After charging 0.70 g (3.0 mmol) of compound L3 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.90 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.3 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was cooledto −78° C. and then 3.0 ml of a titanium tetrachloride solution (0.5mmol/ml heptane solution, 1.50 mmol) was slowly added dropwise. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filteredwith a glass filter. The resulting solid was dissolved and washed in 50ml of methylene chloride, and the insoluble portion was removed byfiltration. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.15 g (0.26 mmol, 17% yield) ofcompound A-3 as yellow brown crystals represented by the formula givenbelow.

[0638]¹H-NMR(CDCl₃): 1.20 (s,18H), 1.41 (s,18H), 6.85-7.05 (m,2H),7.20-7.80 (m, 4H), 8.58 (s, 2H) FD-mass spectrometry: 582 (M+) Elementalanalysis: Ti: 8.2% (8.2) C: 62.1% (61.8), H: 7.1% (7.6), N: 4.7% (4.8)Calculated values in parentheses.

Synthesis Example 10

[0639] Synthesis of Compound B-3

[0640] After charging 0.70 g (3.0 mmol) of compound L3 and 30 ml oftetrahydrofuran into a 100 ml reactor which had been adequately driedand substituted with argon, they were cooled to −78° C. and stirred.After dropwise adding 1.90 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.3 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was cooledto −78° C. and solid zirconium tetrachloride (0.38 g, 1.65 mmol) wasadded. After completion of the addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the solvent was distilled offfrom the reaction solution, the resulting solid was dissolved and washedin 50 ml of methylene chloride, and the insoluble portion was removed byfiltration. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with methylene chloride andhexane and dried under reduced pressure to obtain 0.31 g (0.50 mmol, 30%yield) of compound B-3 as a yellow powder represented by the formulagiven below.

[0641]¹H-NMR(CDCl₃): 1.34 (s,18H), 1.44 (s,18H), 6.79 (dd,2H), 7.11(d,2H), 7.27 (d,2H), 8.34 (s,2H) FD-mass spectrometry: 626 (M+)Elemental analysis: Zr: 15.0% (14.6) C: 52.9 (57.5), H: 7.2 (7.1), N:4.7 (4.8) Calculated values in parentheses.

Synthesis Example 11

[0642] Synthesis of Compound A-4

[0643] After charging 0.50 g (2.02 mmol) of compound L4 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.36 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 2.09 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 2.00 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.00 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 8 hours at room temperature, the reaction solution wasfiltered with a glass filter. The resulting solid was dissolved andwashed in 50 ml of methylene chloride, and the insoluble portion wasremoved by filtration. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with methylenechloride and hexane and dried under reduced pressure to obtain 0.34 g(0.56 mmol, 56% yield) of compound A-4 as a dark brown powderrepresented by the formula given below.

[0644]¹H-NMR(CDCl₃): 7.00-7.90 (m,22H), 8.35-8.55 (m,2H) FD-massspectrometry: 610 (M+) Elemental analysis: Ti: 7.8% (7.8) C: 62.4%(66.8), H: 4.9% (4.4), N: 4.2% (4.6) Calculated values in parentheses.

Synthesis Example 12

[0645] Synthesis of Compound B-4

[0646] After charging 0.46 g (1.86 mmol) of compound L4 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.30 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 2.00 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then solid zirconium tetrachloride (0.21 g, 0.91mmol) was added. After completion of the addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 16 hours at room temperature, 20 ml ofdiethyl ether was added and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.25 g (0.38 mmol, 42% yield) ofcompound B-4 as a yellow-brownish green powder represented by theformula given below.

[0647]¹H-NMR(CDCl₃): 6.90-7.95 (m,22H), 8.40-8.60 (m,2H) FD-massspectrometry: 652 (M+) Elemental analysis: Zr: 14.3% (13.9) Calculatedvalue in parentheses.

Synthesis Example 13

[0648] Synthesis of Compound A-5

[0649] After charging 0.83 g (3.00 mmol) of compound L5 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −780° C. and stirred. Afterdropwise adding 2.00 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.08 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 3.00 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.50 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withmethylene chloride and hexane and dried under reduced pressure to obtain0.07 g (0.10 mmol, 7% yield) of compound A-5 as an ocher powderrepresented by the formula given below.

[0650] FD-mass spectrometry: G66 (M+) Elemental analysis: Ti: 7.3% (7.2)Calculated value in parentheses.

Synthesis Example 14

[0651] Synthesis of Compound B-5

[0652] After charging 0.50 g (1.82 mmol) of compound L5 and 15 ml oftetrahydrofuran into a 100 ml reactor which had been adequately driedand substituted with argon, they were cooled to −78° C. and stirred.After dropwise adding 1.36 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 2.09 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C. and then a 10 ml tetrahydrofuran solution containing azirconium tetrachloride•2THF complex (0.38 g, 1.00 mmol) was addeddropwise. After completion of the dropwise addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 10 hours at room temperature and 4 hours at50° C., the insoluble portion was removed with a glass filter. Thefiltrate was concentrated under reduced pressure and the deposited solidwas reprecipitated with methylene chloride, diethyl ether and hexane anddried under reduced pressure to obtain 0.04 g (0.05 mmol, 5% yield) ofcompound B-5 as a yellow-brownish green powder represented by theformula given below.

[0653] FD-mass spectrometry: 710 (M+) Elemental analysis: Zr: 13.3%(12.8) Calculated value in parentheses.

Synthesis Example 15

[0654] Synthesis of Compound A-6

[0655] After charging 0.93 g (3.01 mmol) of compound L6 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.1 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.23 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C. and then 3.0 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.50 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was recrystallized with hexaneat −78° C. and dried under reduced pressure to obtain 0.41 g (0.56 mmol,37% yield) of compound A-6 as a brown powder represented by the formulagiven below.

[0656]¹H-NMR(CDCl₃): 1.21 (s,18H), 1.30 (s,18H), 6.70-7.70 (m,14H), 8.08(s,2H) FD-mass spectrometry: 734 (M+) Elemental analysis: Ti: 6.6% (6.5)C: 67.9% (68.6), H: 7.4% (7.1), N: 3.9% (3.8) Calculated values inparentheses.

Synthesis Example 16

[0657] Synthesis of Compound B-6

[0658] After charging 0.93 g (3.01 mmol) of compound L6 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.1 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.23 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C. and then solid zirconium tetrachloride (0.35 g, 1.50mmol) was added. After completion of the addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 14 hours at room temperature, 20 ml ofmethylene chloride was added, and the insoluble portion was removed witha glass filter. The filtrate was concentrated under reduced pressure,and the deposited solid was recrystallized with hexane at −78° C. anddried under reduced pressure to obtain 0.55 g (0.71 mmol, 47% yield) ofcompound B-6 as a brownish green powder represented by the formula givenbelow.

[0659]¹H-NMR(CDCl₃): 1.20-1.80 (m,36H), 6.70-7.70 (m,14H), 7.80-7.90(m,2H) FD-mass spectrometry: 776 (M+) Elemental analysis: Zr: 11.2%(11.7) Calculated value in parentheses.

Synthesis Example 17

[0660] Synthesis of Compound A-7

[0661] After charging 1.0 g (3.66 mmol) of compound L7 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to -78° C. and stirred. Afterdropwise adding 2.48 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.84 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixture of 3.66 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.83 mmol) and 20ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the reaction solution was filtered with a glassfilter. The filtrate was concentrated under reduced pressure, and thedeposited solid was reslurried with hexane. The slurry was filtered toremove the solvent, and the solid was dried under reduced pressure toobtain 0.95 g (1.43 mmol, 78% yield) of compound A-7 as a brown powderrepresented by the formula given below.

[0662]¹H-NMR(CDCl₃): 6.90-7.90 (m,26H), 8.00 (s,2H) FD-massspectrometry: 662 (M+) Elemental analysis: Ti: 6.5% (6.5) C: 62.0%(62.2), H: 3.7% (3.8), N: 3.8% (3.8) Calculated values in parentheses.

Synthesis Example 18

[0663] Synthesis of Compound B-7

[0664] After charging 1.0 g (3.66 mmol) of compound L7 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.48 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.84 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixture of zirconium tetrachloride (0.41 g,1.77 mmol) in 30 ml of diethyl ether cooled to −78° C. After completionof the dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, 20 ml of methylene chloride was added, and theinsoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreslurried with hexane. The slurry was filtered to remove the solventand the solid was dried under reduced pressure to obtain 0.94 g (1.33mmol, 73% yield) of compound B-7 as a yellow green powder represented bythe formula given below.

[0665]¹H-NMR(CDCl₃): 7.00-7.90 (m,26H), 8.20 (s,2H) FD-massspectrometry: 704 (M+) Elemental analysis: Zr: 11.5% (11.7) Calculatedvalues in parentheses.

Synthesis Example 19

[0666] Synthesis of Compound A-8

[0667] After charging 1.0 g (2.93 mmol) of compound L8 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.10 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixture containing 2.9 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.45 mmol) and 20ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the reaction solution was filtered with a glassfilter. The filtrate was concentrated under reduced pressure, and thedeposited solid was reslurried with hexane. The slurry was filtered toremove the solvent and the solid was dried under reduced pressure toobtain 1.06 g (1.33 mmol, 91% yield) of compound A-8 as a brown powderrepresented by the formula given below.

[0668]¹H-NMR(CDCl₃): 0.90-1.70 (m,18H), 3.40-3.80 (m,4H), 7.00-7.70(m,20H), 7.80-8.20 (m,2H) FD-mass spectrometry: 798 (M+) Elementalanalysis: Ti: 6.0% (6.0) Calculated value in parentheses.

Synthesis Example 20

[0669] Synthesis of Compound B-8

[0670] After charging 1.0 g (2.93 mmol) of compound L8 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.10 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixture of zirconium tetrachloride (0.34 g,1.44 mmol) in 20 ml of diethyl ether which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 8 hours at room temperature, 20 ml of diethyl ether wasadded, and the insoluble portion was removed with a glass filter. Thefiltrate was concentrated under reduced pressure, and the depositedsolid was reslurried with hexane. The slurry was filtered to remove thesolvent and the solid was dried under reduced pressure to obtain 1.02 g(1.21 mmol, 83% yield) of compound B-8 as a yellow green powderrepresented by the formula given below.

[0671]¹H-NMR(CDCl₃): 0.90-1.80 (m,18H), 3.40-3.90 (m,4H), 6.40-7.90(m,20H), 8.00-8.30 (m,2H) FD-mass spectrometry: 842 (M+) Elementalanalysis: Zr: 11.1% (10.8) Calculated value in parentheses.

Synthesis Example 21

[0672] Synthesis of Compound A-9

[0673] After charging 0.50 g (1.23 mmol) of compound L9 and 15 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.84 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.30 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.2 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.60mmol) and 15 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the reaction solution was filtered witha glass filter. The filtrate was concentrated under reduced pressure,and the deposited solid was reslurried with hexane. The slurry wasfiltered to remove the solvent and the solid was dried under reducedpressure to obtain 0.33 g (0.36 mmol, 58% yield) of compound A-9 as abrown powder represented by the formula given below.

[0674]¹H-NMR(CDCl₃): 1.70-1.90 (m,18H), 6.60-7.80 (m,34H) FD-massspectrometry: 926 (M+) Elemental analysis: Ti: 5.3% (5.2) Calculatedvalue in parentheses.

Synthesis Example 22

[0675] Synthesis of Compound B-9

[0676] After charging 0.50 g (1.23 mmol) of compound L9 and 15 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.84 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.30 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution of zirconiumtetrachloride (0.14 g, 0.60 mmol) and 15 ml of diethyl ether which hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the solvent was distilled off, the resulting solid was dissolved in 50ml of methylene chloride and 10 ml of diethyl ether, and then theinsoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreslurried with hexane. The slurry was filtered to remove the solventand the solid was dried under reduced pressure to obtain 0.19 g (0.20mmol, 32% yield) of compound B-9 as a light yellow powder represented bythe formula given below.

[0677]¹H-NMR(CDCl₃): 1.28-1.52 (m,18H), 6.70-7.76 (m,34H) FD-massspectrometry: 970 (M+) Elemental analysis: Zr: 9.6% (9.4) Calculatedvalue in parentheses.

Synthesis Example 23

[0678] Synthesis of Compound A-10

[0679] After charging 0.32 g (1.03 mmol) of compound L10 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.77 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.19 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution containing 1.0 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 0.50 mmol) and 10ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the reaction solution was filtered with a glassfilter. The filtrate was concentrated under reduced pressure, and thedeposited solid was reprecipitated with methylene chloride and hexaneand dried under reduced pressure to obtain 0.16 g (0.22 mmol, 43% yield)of compound A-10 as a brown powder represented by the formula givenbelow.

[0680]¹H-NMR(CDCl₃): 0.40-0.90 (m,30H), 6.60-7.80 (m,18H) FD-massspectrometry: 739 (M+) Elemental analysis: Ti: 5.3% (5.2) Calculatedvalue in parentheses.

Synthesis Example 24

[0681] Synthesis of Compound A-11

[0682] After charging 0.68 g (2.40 mmol) of compound L11 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.49 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.40 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution containing 2.4 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.20 mmol) and 15ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the solvent of the reaction solution was distilledoff, the resulting solid was dissolved in 50 ml of methylene chloride,and the insoluble portion was filtered off with a glass filter. Thefiltrate was concentrated under reduced pressure, and the depositedsolid was reprecipitated with methylene chloride and hexane at 0° C. anddried under reduced pressure to obtain 0.37 g (0.54 mmol, 45% yield) ofcompound A-11 as a red brown powder.

[0683]¹H-NMR(CDCl₃): 1.20-1.40 (m,9H), 1.50-1.55 (m,9H), 3.70-3.85(m,6H), 6.52-7.40 (m,14H), 8.05-8.20 (m,2H) FD-mass spectrometry: 682(M+) Elemental analysis: Ti: 7.0% (7.0) Calculated value in parentheses.

Synthesis Example 25

[0684] Synthesis of Compound B-11

[0685] After charging 0.64 g (2.26 mmol) of compound L11 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.40 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.26 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution of zirconium tetrachloride•2THF(0.42 g, 1.10 mmol) in 20 ml of tetrahydrofuran which had been cooled to−78° C. After completion of the dropwise addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 15 hours at room temperature, the solvent ofthe reaction solution was distilled off. The resulting solid wasdissolved in 50 ml of methylene chloride, and the insoluble portion wasfiltered off with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withmethylene chloride and hexane and dried under reduced pressure to obtain0.25 g (0.34 mmol, 31% yield) of compound B-11 as a yellow green powderrepresented by the formula given below.

[0686]¹H-NMR(CDCl₃): 1.20-1.60 (m,18H), 3.66-3.86 (m, 6H), 6.50-7.50(m,14H), 8.05-8.20 (m,2H) FD-mass spectrometry: 726 (M+) Elementalanalysis: Zr: 12.4% (12.6) Calculated value in parentheses.

Synthesis Example 26

[0687] Synthesis of Compound A-12

[0688] After charging 1.0 g (2.31 mmol) of compound L12 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.56 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.3 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.15mmol) and 20 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion was filtered offwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reslurried with hexane. The slurrywas filtered to remove the solvent and the solid was dried under reducedpressure to obtain 0.45 g (0.45 mmol, 40% yield) of compound A-12 as ared brown powder.

[0689]¹H-NMR(CDCl₃): 1.30-2.20 (m,24H), 6.20-7.40 (m,34H) 7.50-7.70(m,2H) FD-mass spectrometry: 982 (M+) Elemental analysis: Ti: 5.0% (4.9)Calculated value in parentheses.

Synthesis Example 27

[0690] Synthesis of Compound B-12

[0691] After charging 1.0 g (2.31 mmol) of compound L12 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.56 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution of zirconiumtetrachloride (0.27 g, 1.15 mmol) and 20 ml of diethyl ether which hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with diethyl ether, hexane, heptane and pentane,reslurried and washed, and then dried under reduced pressure to obtain0.02 g (0.02 mmol, 1% yield) of compound B-12 as a yellow green powderrepresented by the formula given below.

[0692]¹H-NMR(CDCl₃): 1.20-2.10 (m,24H), 6.20-7.40 (m,34H), 7.50-8.00(m,2H) FD-mass spectrometry: 1026 (M+) Elemental analysis: Zr: 9.1%(8.9) Calculated value in parentheses.

Synthesis Example 28

[0693] Synthesis of Compound A-13

[0694] After charging 1.10 g (3.26 mmol) of compound L13 and 22 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.2 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.41 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 3.26 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.13mmol) and 22 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the solvent of the reaction solutionwas distilled off, the insoluble portion of the reaction solution wasfiltered off with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withdiethyl ether and pentane and dried under reduced pressure to obtain0.22 g (0.28 mmol, 17% yield) of compound A-13 as a red brown powder.

[0695]¹H-NMR(CDCl₃): 0.60-2.41 (m,44H), 6.70-7.60 (m,34H), 7.91-8.10(m,2H) FD-mass spectrometry: 790 (M+) Elemental analysis: Ti: 6.3% (6.1)Calculated value in parentheses.

Synthesis Example 29

[0696] Synthesis of Compound B-13

[0697] After charging 1.03 g (3.02 mmol) of compound L13 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.10 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution of zirconiumtetrachloride (0.35 g, 1.50 mmol) and 20 ml of diethyl ether which hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, the deposited solid wasrecrystallized with pentane and dried under reduced pressure to obtain0.27 g (0.32 mmol, 21% yield) of compound B-13 as a yellow green powderrepresented by the formula given below.

[0698]¹H-NMR(CDCl₃): 0.30-2.32 (m,44H), 6.70-7.60 (m,14H), 7.90-8.20(m,2H) FD-mass spectrometry: 834 (M+) Elemental analysis: Zr: 10.9%(10.9) Calculated value in parentheses.

Synthesis Example 30

[0699] Synthesis of Compound A-14

[0700] After charging 0.98 g (2.97 mmol) of compound L14 and 30 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 3.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.50mmol) and 15 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion of the reactionsolution was filtered off, the filtered substance was dissolved in 30 mlof diethyl ether and 50 ml of methylene chloride, and the insolubleportion was filtered off with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasrecrystallized with diethyl ether and dried under reduced pressure toobtain 0.66 g (0.85 mmol, 57% yield) of compound A-14 as a dark brownpowder.

[0701]¹H-NMR(CDCl₃): 1.41 (s,18H), 6.70-7.90 (m,24H), 8.18 (s,2H)FD-mass spectrometry: 774 (M+) Elemental analysis: Ti: 6.2% (6.2)Calculated value in parentheses.

Synthesis Example 31

[0702] Synthesis of Compound B-14

[0703] After charging 1.01 g (3.05 mmol) of compound L14 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a tetrahydrofuran solution containingzirconium tetrachloride (0.36 g, 1.52 mmol) which had been cooled to−78° C. After completion of the dropwise addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 8 hours at room temperature, the insolubleportion was removed with a glass filter. The filtrate was concentratedto dryness, and the deposited solid was reprecipitated with methylenechloride and hexane and dried under reduced pressure to obtain 0.61 g(0.74 mmol, 49% yield) of compound B-14 as a fluorescent yellow powderrepresented by the formula given below.

[0704]¹H-NMR(CDCl₃): 1.41 (s,18H), 6.80-7.90 (m,24H), 8.24 (s,2H)FD-mass spectrometry: 818 (M+) Elemental analysis: Zr: 11.0% (11.1)Calculated value in parentheses.

Synthesis Example 32

[0705] Synthesis of Compound A-15

[0706] After charging 0.40 g (1.01 mmol) of compound L15 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.77 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.19 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.50mmol) and 10 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion was filtered offwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.19 g (0.21 mmol,42% yield) of compound A-15 as a red brown powder.

[0707]¹H-NMR(CDCl₃): 0.60-1.30 (m,6H), 6.50-7.80 (m,36H), 7.80-7.90(m,2H) FD-mass spectrometry: 900 (M+) Elemental analysis: Ti: 5.5% (5.3)Calculated value in parentheses.

Synthesis Example 33

[0708] Synthesis of Compound B-15

[0709] After charging 0.40 g (1.02 mmol) of compound L15 and 10 ml oftetrahydrofuran into a 100 ml reactor which had been adequately driedand substituted with argon, they were cooled to −78° C. and stirred.After dropwise adding 0.77 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.19 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. After cooling thesolution to −78° C., solid zirconium tetrachloride (0.12 g, 0.50 mmol)was added. After completion of the addition, stirring was continuedwhile slowly increasing the temperature to room temperature. Afterfurther stirring for 15 hours at room temperature, the solvent of thereaction solution was distilled off. The resulting solid was dissolvedin 50 ml of methylene chloride, and the insoluble portion was removedwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.20 g (0.21 mmol,42% yield) of compound B-15 as a grayish white powder represented by theformula given below.

[0710]¹H-NMR(CDCl₃): 0.70-1.00 (m,6H), 6.60-7.60 (m,36H), 7.70-7.80(m,2H) FD-mass spectrometry: 944 (M+) Elemental analysis: Zr: 9.4% (9.6)Calculated value in parentheses.

Synthesis Example 34

[0711] Synthesis of Compound A-16

[0712] After charging 1.0 g (4.73 mmol) of compound L16 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.2 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 4.96 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 4.7 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 2.35mmol) and 20 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filtered,and the filtered substance was dissolved in 50 ml of methylene chloride.The insoluble portion was removed, the filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withmethylene chloride and hexane and dried under reduced pressure to obtain0.96 g (1.78 mmol, 75% yield) of compound A-16 as a pale brown powder.

[0713]¹H-NMR(CDCl₃): 1.90 (s,6H), 6.50-7.30 (m,16H), 7.90 (s, 2H)FD-mass spectrometry: 538 (M+) Elemental analysis: Ti: 9.0% (8.9)Calculated value in parentheses.

Synthesis Example 35

[0714] Synthesis of Compound B-16

[0715] After charging 1.0 g (4.73 mmol) of compound L16 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.2 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 4.96 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.55g, 2.36 mmol) and 20 ml of diethyl ether which had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. Afterfurther stirring for 15 hours at room temperature, the reaction solutionwas filtered off. The solvent of the filtrate was distilled off, and theresulting solid was recrystallized with diethyl ether, methylenechloride and hexane and dried under reduced pressure to obtain 0.49 g(0.84 mmol, 36% yield) of compound B-16 as a yellow green powderrepresented by the formula given below.

[0716]¹H-NMR(CDCl₃): 2.00 (s,6H), 6.40-7.40 (m,16H), 8.10 (s,2H) FD-massspectrometry: 582 (M+) Elemental analysis: Zr: 15.9% (15.7) Calculatedvalue in parentheses.

Synthesis Example 36

[0717] Synthesis of Compound A-17

[0718] After charging 1.0 g (2.77 mmol) of compound L17 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.87 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.90 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.76 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.38mmol) and 20 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion was filtered offwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reslurried with hexane. The slurrywas filtered to remove the solvent and the solid was dried under reducedpressure to obtain 0.15 g (0.18 mmol, 13% yield) of compound A-17 as abrown powder.

[0719]¹H-NMR(CDCl₃): 3.20-3.80 (m,4H), 6.90-7.81 (m,30H), 8.15 (s,2H)FD-mass spectrometry: 838 (M+) Elemental analysis: Ti: 5.9% (5.7)Calculated value in parentheses.

Synthesis Example 37

[0720] Synthesis of Compound B-17

[0721] After charging 1.0 g (2.77 mmol) of compound L17 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.87 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.90 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.32g, 1.37 mmol) and 20 ml of diethyl ether which had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. Afterfurther stirring for 15 hours at room temperature, the insoluble portionin the reaction solution was removed with a glass filter. The filtratewas concentrated under reduced pressure, and the deposited solid wasreslurried with hexane. The slurry was filtered to remove the solventand the solid was dried under reduced pressure to obtain 0.71 g (0.88mmol, 58% yield) of compound B-17 as a yellow green powder representedby the formula given below.

[0722]¹H-NMR(CDCl₃): 3.30-3.80 (m,4H), 6.71-7.72 (m,30H), 8.25 (s,2H)FD-mass spectrometry: 882 (M+) Elemental analysis: Zr: 10.6% (10.3)Calculated value in parentheses.

Synthesis Example 38

[0723] Synthesis of Compound A-18

[0724] After charging 0.59 g (2.20 mmol) of compound L18 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.49 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.31 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.2 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.10mmol) and 10 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the mixture was concentratedto dryness, and the resulting solid was dissolved in 20 ml of methylenechloride. The insoluble portion was filtered off with a glass filter,the filtrate was concentrated under reduced pressure, and the depositedsolid was reprecipitated with diethyl ether and hexane at −78° C. anddried under reduced pressure to obtain 0.27 g (0.41 mmol, 37% yield) ofcompound A-18 as a brown powder.

[0725]¹H-NMR(CDCl₃): 1.22 (s,18H), 2.40 (s,6H), 6.44-7.80 (m,14H), 8.21(s,2H) FD-mass spectrometry: 650 (M+) Elemental analysis: Ti: 7.1% (7.4)Calculated value in parentheses.

Synthesis Example 39

[0726] Synthesis of Compound B-18

[0727] After charging 0.60 g (2.25 mmol) of compound L18 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.26 g,1.12 mmol) in 10 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 8 hours at room temperature, the solvent of the reactionsolution was distilled off. The resulting solid was dissolved in 20 mlof methylene chloride, and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.16 g (0.24 mmol, 21% yield) ofcompound B-18 as a yellow green powder represented by the formula givenbelow.

[0728]¹H-NMR(CDCl₃): 1.13 (s,18H), 2.39 (s,6H), 6.50-7.75 (m,14H), 8.26(s,2H) FD-mass spectrometry: 694 (M+) Elemental analysis: Zr: 13.1%(13.1) Calculated value in parentheses.

Synthesis Example 40

[0729] Synthesis of Compound B-19

[0730] After charging 0.70 g (2.25 mmol) of compound L19 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyIncreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.26 g,1.12 mmol) in 10 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the solvent of the reactionsolution was distilled off. The resulting solid was dissolved in 20 mlof methylene chloride, and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.16 g (0.20 mmol, 18% yield) ofcompound B-19 as a yellow green powder represented by the formula givenbelow.

[0731]¹H-NMR(CDCl₃): 1.43 (s,18H), 1.47 (s,18H), 6.90-7.60 (m,14H), 8.40(s,2H) FD-mass spectrometry: 778 (M+) Elemental analysis: Zr: 12.1%(11.7) Calculated value in parentheses.

Synthesis Example 41

[0732] Synthesis of Compound B-20

[0733] After charging 0.63 g (2.25 mmol) of compound L20 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.26 g,1.12 mmol) in 10 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the solvent of the reactionsolution was distilled off. The resulting solid was dissolved in 25 mlof methylene chloride, and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.35 g (0.48 mmol, 43% yield) ofcompound B-20 as a yellow powder represented by the formula given below.

[0734]¹²H-NMR(CDCl₃): 1.40 (s,18H), 1.50 (s,18H), 2.21 (s,12H),6.70-7.40 (m,12H), 8.33 (s,2H) FD-mass spectrometry: 720 (M+) Elementalanalysis: Zr: 12.8% (12.6) Calculated value in parentheses.

Synthesis Example 42

[0735] Synthesis of Compound A-21

[0736] After charging 0.80 g (2.50 mmol) of compound L21 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.7 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.64 mmol) over 5 minutes, the temperature was slowlyincreased to 0° C., and stirring was continued for 4 hours at 0° C. toprepare a lithium salt solution. The solution was then slowly addeddropwise to a mixed solution containing 2.5 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.25 mmol) and 10ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the mixture was concentrated to dryness, and theresulting solid was dissolved in 50 ml of diethyl ether and 60 ml ofmethylene chloride. The insoluble portion was filtered off with a glassfilter, the filtrate was concentrated under reduced pressure, and thedeposited solid was recrystallized with diethyl ether and dried underreduced pressure to obtain 0.07 g (0.09 mmol, 8% yield) of compound A-21as a red brown powder.

[0737]¹H-NMR(CDCl₃): 1.34 (s,18H), 6.75-7.75 (m,14H), 8.10 (s,2H)FD-mass spectrometry: 758 (M+) Elemental analysis: Ti: 6.5% (6.3)Calculated value in parentheses.

Synthesis Example 43

[0738] Synthesis of Compound B-21

[0739] After charging 1.03 g (3.20 mmol) of compound L21 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to −15° C. and stirring was continued for 2 hours at −15° C.to prepare a lithium salt solution. The solution was then added dropwiseto a solution of zirconium tetrachloride (0.36 g, 1.54 mmol) in 10 ml oftetrahydrofuran which had been cooled to −78° C. After completion of thedropwise addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 15 hours atroom temperature, the solvent of the reaction solution was distilledoff. The residue was dissolved in 20 ml of toluene, and the reaction wascontinued for 3 hours under reflux conditions. The solvent was distilledoff, the resulting solid was dissolved in 50 ml of methylene chloride,and the insoluble portion was removed with a glass filter. The filtratewas concentrated under reduced pressure, and the deposited solid wasreprecipitated with diethyl ether and hexane and dried under reducedpressure to obtain 0.33 g (0.41 mmol, 27% yield) of compound B-21 as anocher powder represented by the formula given below.

[0740]¹H-NMR(CDCl₃): 1.24 (s,18H), 6.80-7.78 (m,14H), 3.15 (s,2H)FD-mass spectrometry: 802 (M+) Elemental analysis: Zr: 11.7% (11.4)Calculated value in parentheses.

Synthesis Example 44

[0741] Synthesis of Compound A-22

[0742] After charging 0.50 g (1.77 mmol) of compound L22 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.86 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.77 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.89mmol) and 50 ml of diethyl ether which had been cooled to −78° C.

[0743] After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. Afterfurther stirring for 15 hours at room temperature, the reaction solutionwas filtered with a glass filter. After washing the filtered substancewith diethyl ether, it was dissolved in methylene chloride. Theinsoluble portion was removed, the filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withdiethyl ether and hexane at −78° C. and dried under reduced pressure toobtain 0.31 g (0.45 mmol, 51% yield) of compound A-22 as a brown powder.

[0744]¹H-NMR(CDCl₃): 0.70-1.80 (m,18H), 3.50-4.00 (m,6H), 6.40-7.70(m,14H), 8.05 (s,2H) FD-mass spectrometry: 682 (M+) Elemental analysis:Ti: 7.3% (7.0) Calculated value in parentheses.

Synthesis Example 45

[0745] Synthesis of Compound B-22

[0746] After charging 0.50 g (1.77 mmol) of compound L22 and 25 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.86 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.21g, 0.99 mmol) in 10 ml of diethyl ether and 60 ml of tetrahydrofuranwhich had been cooled to −78° C. After completion of the dropwiseaddition, stirring was continued while slowly increasing the temperatureto room temperature. After further stirring for 15 hours at roomtemperature, the solvent of the reaction solution was distilled off. Theresulting solid was reslurried with 70 ml of hexane, and the insolubleportion was separated off with a glass filter. The filtered substancewas dissolved in 100 ml of diethyl ether and 70 ml of hexane. Afterremoving out the insoluble portion, the filtrate was concentrated underreduced pressure. The deposited solid was washed with hexane and driedunder reduced pressure to obtain 0.08 g (0.11 mmol, 11% yield) ofcompound B-22 as a yellow green powder represented by the formula givenbelow.

[0747]¹H-NMR(CDCl₃): 1.40 (s,18H), 3.75 (s,6H), 6.40-7.70 (m,14H), 8.10(s,2H) FD-mass spectrometry: 726 (M+) Elemental analysis: Zr: 12.3%(12.6) Calculated value in parentheses.

Synthesis Example 46

[0748] Synthesis of Compound A-23

[0749] After charging 1.01 g (4.33 mmol) of compound L23 and 22 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.9 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 4.50 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 4.25 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 2.13mmol) and 20 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filtered,the filtrate was concentrated to dryness, and the resulting solid wasreprecipitated with methylene chloride, diethyl ether and hexane anddried under reduced pressure to obtain 0.26 g (0.44 mmol, 21% yield) ofcompound A-23 as a brown powder.

[0750]¹H-NMR(CDCl₃): 0.82-1.40 (m,12H), 2.90-3.30 (m,2H), 6.60-7.40(m,16H), 8.10 (s,2H) FD-mass spectrometry: 594 (M+) Elemental analysis:Ti: 8.0% (8.0) Calculated value in parentheses.

Synthesis Example 47

[0751] Synthesis of Compound B-23

[0752] After charging 1.02 g (4.25 mmol) of compound L23 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.43 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 5.32 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.50g, 2.15 mmol) and 20 ml of diethyl ether which had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. Afterfurther stirring for 15 hours at room temperature, the insoluble portionwas removed with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withdiethyl ether, methylene chloride and hexane and dried under reducedpressure to obtain 0.61 g (0.96 mmol, 45% yield) of compound B-23 as ayellow green powder represented by the formula given below.

[0753]¹H-NMR(CDCl₃): 0.80-1.30 (m,12H), 2.90-3.25 (m,2H), 6.72-7.43(m,16H), 8.20 (s,2H) FD-mass spectrometry: 638 (M+) Elemental analysis:Zr: 14.0% (14.3) Calculated value in parentheses.

Synthesis Example 48

[0754] Synthesis of Compound A-24

[0755] After charging 0.52 g (2.05 mmol) of compound L24 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.36 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.11 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt slurry. The solution wasslowly added dropwise to a mixed solution containing 2.04 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.02mmol), 40 ml of diethyl ether and 20 ml of tetrahydrofuran which hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the solvent of the reaction solution was distilled off. The resultingsolid was reslurried with 100 ml of diethyl ether, and the insolubleportion was separated off with a glass filter. The filtered substancewas washed with diethyl ether and dissolved in methylene chloride. Afterremoving the insoluble portion, the filtrate was concentrated underreduced pressure, and the deposited solid was washed with hexane anddried under reduced pressure to obtain 0.12 g (0.19 mmol, 19% yield) ofcompound A-24 as an orange powder.

[0756]¹H-NMR(CDCl₃): 0.80-2.30 (m,18H), 6.30-9.20 (m,14H), 8.35 (brs,2H)FD-mass spectrometry: 624 (M+) Elemental analysis: Ti: 8.1% (7.7)Calculated value in parentheses.

Synthesis Example 49

[0757] Synthesis of Compound B-24

[0758] After charging 0.76 g (2.99 mmol) of compound L24 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.91 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.08 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt slurry. The solution was thenadded dropwise to a mixed solution of zirconium tetrachloride•2THFcomplex (0.563 g, 1.49 mmol) in 80 ml of tetrahydrofuran which had beencooled to −78° C. After completion of the dropwise addition, stirringwas continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature, 50ml of toluene was added, and the reaction solution was heated at 80° C.for 10 hours and then at 90° C. for 30 hours while stirring. The solventof the reaction solution was distilled off, the resulting solid wasreslurried with 150 ml of diethyl ether, and the insoluble portion wasseparated off with a glass filter. After washing the filtered substancewith diethyl ether, it was dissolved in methylene chloride, theinsoluble portion was removed out, and then the filtrate wasconcentrated under reduced pressure. The deposited solid was washed withhexane and dried under reduced pressure to obtain 0.43 g (0.64 mmol, 43%yield) of compound B-24 as a yellow powder represented by the formulagiven below.

[0759]¹H-NMR(CDCl₃): 0.60-2.30 (m,18H), 6.30-9.40 (m,14H), 8.35 (brs,2H) FD-mass spectrometry: 668 (M+) Elemental analysis: Zr: 13.2% (13.6)Calculated value in parentheses.

Synthesis Example 50

[0760] Synthesis of Compound A-25

[0761] After charging 0.50 g (1.93 mmol) of compound L25 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.42 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.20 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasslowly added dropwise to a mixed solution containing 1.93 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.97mmol) and 50 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filteredwith a glass filter, and the filtered substance was washed with diethylether and dissolved in methylene chloride. After removing the insolubleportion, the filtrate was concentrated under reduced pressure, and thedeposited solid was washed with hexane and dried under reduced pressureto obtain 0.11 g (0.17 mmol, 18% yield) of compound A-25 as a red brownpowder.

[0762]¹H-NMR(CDCl₃): 1.65 (s,18H), 0.50-2.40 (m,20H), 3.85 (brdt,2H),6.90-7.70 (m,6H), 8.20 (s,2H) FD-mass spectrometry: 634 (M+) Elementalanalysis: Ti: 7.6% (7.5) Calculated value in parentheses

Synthesis Example 51

[0763] Synthesis of Compound B-25

[0764] After charging 0.50 g (1.93 mmol) of compound L25 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.42 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.20 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.23 g,0.99 mmol) in 50 ml of diethyl ether which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered with a glass filter, and the filtrate was concentrated underreduced pressure. The deposited solid was washed with hexane and driedunder reduced pressure to obtain 0.28 g (0.41 mmol, 43% yield) ofcompound B-25 as an ocher powder represented by the formula given below.

[0765]¹H-NMR(CDCl₃): 1.65 (s,18H), 0.70-2.50 (m,20H), 3.85 (brdt,2H),6.70-7.70 (m,6H), 8.25 (s,2H) FD-mass spectrometry: 678 (M+) Elementalanalysis: Zr: 13.3% (13.4) calculated value in parentheses.

Synthesis Example 52

[0766] Synthesis of Compound A-26

[0767] After charging 0.61 g (2.28 mmol) of compound L26 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.6 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.48 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.2 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.10mmol) and 10 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 12 hours at room temperature, the insoluble portion wasfiltered out with a glass filter, the filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withdiethyl ether and hexane at −78° C. and dried under reduced pressure toobtain 0.36 g (0.55 mmol, 51% yield) of compound A-26 as a brown powder.

[0768]¹H-NMR(CDCl₃): 1.33 (s,18H), 2.14 (s,6H), 6.60-7.68 (m,14H), 8.03(s,2H) FD-mass spectrometry: 650 (M+) Elemental analysis: Ti: 7.4% (7.3)Calculated value in parentheses.

Synthesis Example 53

[0769] Synthesis of Compound B-26

[0770] After charging 0.61 g (2.28 mmol) of compound L26 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.6 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.48 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.27 g,1.15 mmol) in 10 ml of diethyl ether which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 12 hours at room temperature, the insoluble portion wasremoved with a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.14 g (0.20 mmol,18% yield) of compound B-26 as a yellow green powder represented by theformula given below.

[0771]¹H-NMR(CDCl₃): 1.31 (s,18H), 2.14 (s,6H), 6.69-7.65 (m,14H), 8.09(s,2H) FD-mass spectrometry: 694 (M+) Elemental analysis: Zr: 13.1%(13.1) Calculated value in parentheses.

Synthesis Example 54

[0772] Synthesis of Compound A-27

[0773] After charging 0.30 g (1.00 mmol) of compound L27 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.65 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.00 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.50mmol) and 10 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After first stirring for12 hours at room temperature and then stirring for one hour underreflux, the insoluble portion was filtered out with a glass filter. Thefiltrate was concentrated under reduced pressure, and the depositedsolid was reprecipitated with diethyl ether and hexane and dried underreduced pressure to obtain 0.18 g (0.25 mmol, 50% yield) of compoundA-27 as an orange powder.

[0774]¹H-NMR(CDCl₃): 1.13 (s,18H), 1.25 (brd,6H), 1.28 (brd,6H), 3.29(brdq,2H), 6.45-6.70 (m,2H), 6.80-7.20 (m,4H), 7.20-7.50 (m,8H), 8.23(s,2H) FD-mass spectrometry: 706 (M+) Elemental analysis: Ti: 6.8% (6.8)Calculated value in parentheses.

Synthesis Example 55

[0775] Synthesis of Compound B-27

[0776] After charging 0.95 g (3.20 mmol) of compound L27 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.08 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.37 g,1.60 mmol) in 10 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After firststirring for 12 hours at room temperature and then stirring for 6 hoursunder reflux, the solvent of the reaction solution was distilled off.The resulting solid was dissolved in 50 ml of methylene chloride, andthe insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with methylene chloride and hexane and dried underreduced pressure to obtain 0.18 g (0.24 mmol, 15% yield) of compoundB-27 as a yellow powder.

[0777]¹H-NMR(CDCl₃): 1.10 (s,18H), 1.10-1.40 (m,12H), 3.20-3.30 (m,2H),6.30-6.60 (m,2H), 6.70-7.10-7.60 (m,8H), 8.28 (s;2H) FD-massspectrometry: 750 (M+) Elemental analysis: Zr: 12.0% (12.2) C: 63.5%(64.0) H: 6.6% (6.4) N: 3.5% (3.7) Calculated values in parentheses.

Synthesis Example 56

[0778] Synthesis of Compound A-28

[0779] After charging 0.50 g (1.37 mmol) of compound L28 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.92 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.43 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.37 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane, 0.69 mmol) and 40ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the reaction solution was filtered with a glassfilter, the filtered substance was washed with diethyl ether, and thenthe insoluble portion was removed out by filtration. The filtrate wasconcentrated under reduced pressure, and the deposited solid was washedwith hexane and dried under reduced pressure to obtain 0.17 g (0.20mmol, 29% yield) of compound A-28 as a brown powder.

[0780]¹H-NMR(CDCl₃): 0.70-1.40 (m,54H), 6.65-7.75 (m,12H), 8.35 (s,2H)FD-mass spectrometry: 846 (M+) Elemental analysis: Ti: 5.5% (5.7)Calculated value in parentheses.

Synthesis Example 57

[0781] Synthesis of Compound B-28

[0782] After charging 0.50 g (1.37 mmol) of compound L28 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.92 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.43 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.16g, 0.69 mmol) in 20 ml of anhydrous diethyl ether and 50 ml oftetrahydrofuran which had been cooled to −78° C. After completion of thedropwise addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 12 hours atroom temperature, the solvent of the reaction solution was distilledoff. The resulting solid was reslurried with diethyl ether, theinsoluble portion was removed off with a glass filter, and the filtratewas concentrated under reduced pressure. The deposited solid wasreprecipitated with hexane at −78° C. and dried under reduced pressureto obtain 0.26 g (0.29 mmol, 43% yield) of compound B-28 as a yellowpowder represented by the formula given below.

[0783]¹H-NMR(CDCl₃): 0.80-1.30 (m,54H), 6.65 (m,12H), 8.35 (s,2H)FD-mass spectrometry: 890 (M+) Elemental analysis: Zr: 9.9% (10.2)Calculated value in parentheses.

Synthesis Example 58

[0784] Synthesis of Compound A-29

[0785] After charging 0.60 g (1.79 mmol) of compound L29 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.17 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.81 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.79 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.90mmol) and 50 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After stirring for 12hours at room temperature, the reaction solution was filtered with aglass filter to remove the insoluble portion. The filtrate wasconcentrated under reduced pressure, and the deposited solid was washedwith hexane and dried under reduced pressure to obtain 0.10 g (0.13mmol, 14% yield) of compound A-29 as a red brown powder.

[0786]¹H-NMR(CDCl₃): 0.80-2.30 (m,20H), 1.55 (s,18H), 3.65 (brdt,2H),6.60-8.10 (m,16H) FD-mass spectrometry: 786 (M+) Elemental analysis: Ti:6.4% (6.1) Calculated value in parentheses.

Synthesis Example 59

[0787] Synthesis of Compound B-29

[0788] After charging 0.50 g (1.48 mmol) of compound L29 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.02 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.64 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride•2THFcomplex (0.26 g, 0.69 mmol) in 40 ml of tetrahydrofuran which had beencooled to −78° C. After completion of the dropwise addition, stirringwas continued while slowly increasing the temperature to roomtemperature. After further stirring for 8 hours at room temperature, 70ml of toluene was added, the reaction solution was heated at 80° C. for20 hours while stirring. The solvent of the reaction solution wasdistilled off, the resulting solid was reslurried with 50 ml of diethylether. The slurry was filtered with a glass filter to remove off theinsoluble portion, and then the filtrate was concentrated under reducedpressure. The deposited solid was reprecipitated with hexane at −78° C.and dried under reduced pressure to obtain 0.04 g (0.05 mmol, 7% yield)of compound B-29 as a yellowish white powder represented by the formulagiven below.

[0789]¹H-NMR(CDCl₃): 0.90-1.90 (m,20H), 1.55 (s,18H), 3.25 (brdt,2H),6.40-7.90 (m,16H) FD-mass spectrometry: 830 (M+) Elemental analysis: Zr:11.3% (11.0) Calculated value in parentheses.

Synthesis Example 60

[0790] Synthesis of Compound A-30

[0791] After charging 0.51 g (1.86 mmol) of compound L30 and 50 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution containing 1.85 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.93mmol) and 60 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. Further stirringfor 8 hours at room temperature, the reaction solution was heated at 60°C. for 8 hours while stirring, and the solvent was then distilled off.The resulting solid was reslurried with diethyl ether and filtered witha glass filter, and the filtered substance was washed with diethyl etherand then dissolved in methylene chloride. After removal of the insolubleportion by filtration, the filtrate was concentrated under reducedpressure, and the deposited solid was washed with hexane and dried underreduced pressure to obtain 0.14 g (0.21 mmol, 23% yield) of compoundA-30 as a red orange powder.

[0792]¹H-NMR(CDCl₃): 1.10-2.10 (m,20H), 1.45 (s,18H), 2.40 (s,6H), 3.85(brdt,2H), 6.70-7.70 (m,6H) FD-mass spectrometry: 662 (M+) Elementalanalysis: Ti: 7.1% (7.2) Calculated value in parentheses.

Synthesis Example 61

[0793] Synthesis of Compound B-30

[0794] After charging 0.51 g (1.86 mmol) of compound L30 and 50 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasadded dropwise to a solution of zirconium tetrachloride (0.22 g, 0.94mmol) in 60 ml of tetrahydrofuran which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 12 hours at room temperature, 60 ml of toluene was added, and thereaction solution was heated at 85° C. for 12 hours while stirring.

[0795] The solvent of the reaction solution was distilled off. Theresulting solid was reslurried with 100 ml of diethyl ether, the slurrywas filtered with a glass filter to remove off the insoluble portion,and then the filtrate was concentrated under reduced pressure. Thedeposited solid was washed with hexane and dried under reduced pressureto obtain 0.10 g (0.14 mmol, 15% yield) of compound B-30 as a milkywhite powder represented by the formula given below.

[0796]¹H-NMR(CDCl₃): 0.80-2.10 (m,20H), 1.45 (s,18H), 2.40 (s,6H), 3.75(brdt,2H), 6.50-7.80 (m,6H) FD-mass spectrometry: 704 (M+) Elementalanalysis: Zr: 13.3% (12.9) Calculated value in parentheses.

Synthesis Example 62

[0797] Synthesis of Compound A-31

[0798] After charging 1.00 g (4.22 mmol) of compound L31 and 20 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.75 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 4.43 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 4.22 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 2.11mmol) and 20 ml of diethyl ether which had been cooled to −78° C.

[0799] After completion of the dropwise addition, stirring was continuedwhile-slowly increasing the temperature to room temperature. Afterstirring for 12 hours at room temperature, the reaction solution wasfiltered with a glass filter. The filtered substance was dissolved in 50ml of methylene chloride, and the insoluble portion was removed. Thefiltrate was evaporated to dryness under reduced pressure, and theresulting solid was reprecipitated with methylene chloride and diethylether and dried under reduced pressure to obtain 0.90 g (1.55 mmol, 72%yield) of compound A-31 as a brown powder.

[0800]¹H-NMR(CDCl₃): 6.70-7.40 (m,16H), 7.90-8.20 (m,2H) FD-massspectrometry: 578 (M+) Elemental analysis: Ti: 8.0% (8.3) Calculatedvalue in parentheses.

Synthesis Example 63

[0801] Synthesis of Compound B-31

[0802] After charging 1.20 g (5.18 mmol) of compound L31 and 24 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.38 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 5.44 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution containing zirconiumtetrachloride (0.60 g, 2.57 mmol) and 24 ml of diethyl ether which hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After stirring for 12 hours at room temperature, thereaction solution was filtered with a glass filter. The filteredsubstance was dissolved in 60 ml of methylene chloride and the insolubleportion was removed. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with methylenechloride and hexane and dried under reduced pressure to obtain 0.20 g(0.32 mmol, 12% yield) of compound B-31 as a green powder.

[0803]¹H-NMR(CDCl₃): 6.70-7.45 (m,16H), 7.90-8.25 (m,2H) FD-massspectrometry: 621 (M+) Elemental analysis: Zr: 14.9% (14.6) Calculatedvalue in parentheses.

Synthesis Example 64

[0804] Synthesis of Compound A-32

[0805] After charging 1.00 g (5.05 mmol) of compound L32 and 50 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.25 ml of n-butyllithium (1.63 mmol/ml n-hexanesolution, 5.30 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 2.52 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.26 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 12 hours at room temperature, the reaction solution wasfiltered with a glass filter and the filtered substance was washed withdiethyl ether followed by dissolution in methylene chloride. Afterremoval of the insoluble portion, the filtrate was concentrated underreduced pressure, and the deposited solid was washed with hexane anddried under reduced pressure to obtain 0.23 g (0.45 mmol, 18% yield) ofcompound A-32 as an orange powder.

[0806] FD-mass spectrometry: 512 (M+)

Synthesis Example 65

[0807] Synthesis of Compound A-33

[0808] After charging 1.09 g (4.39 mmol) of compound L33 and 70 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.80 ml of n-butyllithium (1.63 mmol/ml n-hexanesolution, 4.56 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 8.78 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 4.39 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 12 hours at room temperature, the reaction solution wasfiltered with a glass filter and the filtered substance was washed withdiethyl ether followed by dissolution in methylene chloride. Afterremoval of the insoluble portion, the filtrate was concentrated underreduced pressure, and the deposited solid was washed with diethyl etherand dried under reduced pressure to obtain 0.22 g (0.36 mmol, 16% yield)of compound A-33 as a brown powder.

[0809] FD-mass spectrometry: 612 (M+)

Synthesis Example 66

[0810] Synthesis of Compound A-34

[0811] After charging 0.60 g (2.13 mmol) of compound L34 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.75 ml of n-butyllithium (1.63 mmol/ml n-hexanesolution, 4.48 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 0.71 g (2.13 mmol) of a titaniumtetrachloride•tetrahydrofuran complex was slowly added. After completionof the addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 8 hours atroom temperature, the reaction solution was filtered with a glass filterand the filtered substance was washed with diethyl ether followed bydissolution in methylene chloride. After removal of the insolubleportion, the filtrate was concentrated under reduced pressure, and thedeposited solid was washed with hexane and dried under reduced pressureto obtain 0.19 g (0.48 mmol, 23% yield) of compound A-34 as a redpowder.

[0812] FD-mass spectrometry: 398 (M+)

Synthesis Example 67

[0813] Synthesis of Compound A-35

[0814] After charging 0.19 g of sodium hydride (60 wt % product, 4.75mmol) and 50 ml of tetrahydrofuran into a 100 ml reactor which had beenadequately dried and substituted with argon, a solution of 1.00 g (2.30mmol) of compound L35 in 20 ml of tetrahydrofuran was added dropwiseover 5 minutes while stirring at room temperature, after which thetemperature was slowly increased to room temperature, and stirring wascontinued for 2 hours at 50° C. to prepare a sodium salt solution. Thesolution was then slowly added dropwise to a solution of 0.77 g (2.31mmol) of a titanium tetrachloride•tetrahydrofuran complex in 50 ml oftetrahydrofuran while stirring at room temperature. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the reaction solution was filtered with a glassfilter and the filtered substance was washed with diethyl ether followedby removal of the insoluble portion. The filtrate was concentrated underreduced pressure, the deposited solid was reslurried with diethyl ether,the reaction solution was filtered with a glass filter. The filteredsubstance was washed with diethyl ether and dissolved in methylenechloride, and the impurities were removed. The filtrate was concentratedunder reduced pressure, and the deposited solid was washed with hexaneand dried under reduced pressure to obtain 1.10 g (2.00 mmol, 87% yield)of compound A-35 as a red orange powder.

[0815] FD-mass spectrometry: 550 (M+)

Synthesis Example 68

[0816] Synthesis of Compound A-36

[0817] After charging 0.19 g of sodium hydride (60 wt % product, 4.75mmol) and 50 ml of tetrahydrofuran into a 100 ml reactor which had beenadequately dried and substituted with argon, a solution of 1.00 g (2.23mmol) of compound L36 in 20 ml of tetrahydrofuran was added dropwiseover 5 minutes while stirring at room temperature, after which thetemperature was slowly increased to room temperature, and stirring wascontinued for 2 hours at 50° C. to prepare a sodium salt solution. Thesolution was cooled to −78° C., and then 4.50 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 2.25 mmol) wasslowly added dropwise. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 8 hours at room temperature, thereaction solution was filtered with a glass filter and the filteredsubstance was washed with diethyl ether and dissolved in methylenechloride. After removal of the insoluble portion, the filtrate wasconcentrated under reduced pressure, and the deposited solid was washedwith hexane and dried under reduced pressure to obtain 0.55 g (0.97mmol, 44% yield) of compound A-36 as an orange powder.

[0818] FD-mass spectrometry: 564 (M+)

Synthesis Example 69

[0819] Synthesis of Compound B-37

[0820] After charging 0.30 g of sodium hydride (60 wt % product, 7.50mmol) and 50 ml of tetrahydrofuran into a 100 ml reactor which had beenadequately dried and substituted with argon, a solution of 1.00 g (3.16mmol) of compound L37 in 20 ml of tetrahydrofuran was added dropwiseover 5 minutes while stirring at room temperature, after which thetemperature was slowly increased to room temperature, and stirring wascontinued for 2 hours at 60° C. to prepare a sodium salt solution. Thesolution was then slowly added dropwise to a solution of 1.19 g (3.15mmol) of zirconium tetrachloride•2THF complex in 50 ml oftetrahydrofuran while stirring at room temperature. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the reaction solution was filtered with a glassfilter, the filtered substance was washed with tetrahydrofuran and theinsoluble portion was removed. The filtrate was concentrated underreduced pressure to about ⅓, the deposited solid was filtered with aglass filter, and the filtered substance was washed with coldtetrahydrofuran and dried under reduced pressure to obtain 1.00 g (2.10mmol, 66% yield) of compound B-37 as a yellow powder.

[0821] FD-mass spectrometry: 474 (M+)

Synthesis Example 70

[0822] Synthesis of Compound B-38

[0823] After charging 0.23 g of sodium hydride (60 wt % product, 5.75mmol) and 50 ml of tetrahydrofuran into a 100 ml reactor which had beenadequately dried and substituted with argon, a solution of 1.00 g (2.73mmol) of compound L38 in 20 ml of tetrahydrofuran was added dropwiseover 5 minutes while stirring at room temperature, after which thetemperature was slowly increased to room temperature, and stirring wascontinued for 2 hours at 50° C. to prepare a sodium salt solution. Thesolution was then slowly added dropwise to a solution of 1.03 g (2.73mmol) of zirconium tetrachloride•2THF complex in 50 ml oftetrahydrofuran while stirring at room temperature. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the reaction solution was filtered with a glassfilter, the filtered substance was washed with tetrahydrofuran and theinsoluble portion was removed by filtration. The filtrate was allowed tostand for 2 hours, upon which a solid was deposited. The deposited solidwas filtered with a glass filter, and the filtered substance was washedwith cold tetrahydrofuran and dried under reduced pressure to obtain1.15 g (2.18 mmol, 80% yield) of compound B-38 as a yellow powder.

[0824] FD-mass spectrometry: 524 (M+)

Synthesis Example 71

[0825] Synthesis of Compound A-39

[0826] After charging 0.50 g (1.87 mmol) of compound L39 and 50 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasslowly added dropwise to a mixed solution containing 1.87 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.94mmol) and 70 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the reaction solution was filtered witha glass filter, and the filtered substance was washed with diethyl etherand then dissolved in methylene chloride. The insoluble portion wasremoved, the filtrate was then concentrated under reduced pressure, andthe deposited solid was washed with hexane and dried under reducedpressure to obtain 0.11 g (0.17 mmol, 18% yield) of compound A-39 as ared powder.

[0827]¹H-NMR(CDCl₃): 1.65 (s,18H), 4.65 (d,2H), 5.00 (d,2H), 6.75-7.70(m,16H), 7.75 (s,2H) FD-mass spectrometry: 650 (M+) Elemental analysis:Ti: 7.2% (7.3) Calculated value in parentheses.

Synthesis Example 72

[0828] Synthesis of Compound B-39

[0829] After charging 0.50 g (1.87 mmol) of compound L39 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride•2THFcomplex (0.352 g, 0.93 mmol) in 50 ml of tetrahydrofuran which had beencooled to −78° C. After completion of the dropwise addition, stirringwas continued while slowly increasing the temperature to roomtemperature. After further stirring for 8 hours at room temperature, thereaction solution was heated at 60° C. for 3 hours while stirring, andthe solvent was then distilled off. The resulting solid was reslurriedwith 50 ml of diethyl ether and the insoluble portion was separated offwith a glass filter. The filtered substance was washed with 100 ml ofdiethyl ether and dissolved in methylene chloride, the insoluble portionwas removed off, and the filtrate was concentrated under reducedpressure. The deposited solid was washed with hexane and dried underreduced pressure to obtain 0.30 g (0.43 mmol, 46% yield) of compoundB-39 as a yellowish white powder represented by the formula given below.

[0830]¹H-NMR(CDCl₃): 1.60 (s,18H), 4.65 (d,2H), 4.95 (d,2H), 6.70-7.70(m,16H), 7.85 (s,2H) FD-mass spectrometry: 694 (M+) Elemental analysis:Zr: 12.9% (13.1) Calculated value in parentheses.

Synthesis Example 73

[0831] Synthesis of Compound A-40

[0832] After charging 0.58 g (2.02 mmol) of compound L40 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.50 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.00 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.00mmol) and 80 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the reaction solution was filtered witha glass filter, the insoluble portion was removed, and the filtrate wasconcentrated under reduced pressure. The deposited solid wasreprecipitated with hexane at −78° C. and dried under reduced pressureto obtain 0.19 g (0.28 mmol, 28% yield) of compound A-40 as a red orangepowder.

[0833]¹H-NMR(CDCl₃): 0.80-1.80 (m,18H), 6.50-7.90 (m,14H), 8.00-8.20(m,2H) FD-mass spectrometry: 692 (M+) Elemental analysis: Ti: 7.0% (6.9)Calculated value in parentheses.

Synthesis Example 74

[0834] Synthesis of Compound B-40

[0835] After charging 0.58 g (2.02 mmol) of compound L40 and 40 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.50 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing a zirconiumtetrachloride•2THF complex (0.38 g, 1.00 mmol) and 80 ml oftetrahydrofuran which had been cooled to −78° C. After completion of thedropwise addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 8 hours atroom temperature, the solvent of the reaction solution was distilledoff. The resulting solid was reslurried with 150 ml of diethyl ether,the insoluble portion was removed off with a glass filter, and then thefiltrate was concentrated under reduced pressure. The deposited solidwas reprecipitated with hexane at −78° C. and dried under reducedpressure to obtain 0.23 g (0.31 mmol, 31% yield) of compound B-40 as ayellow powder represented by the formula given below.

[0836]¹H-NMR(CDCl₃): 0.80-1.70 (m,18H), 6.50-7.90 (m,14H), 8.20 (s,2H)FD-mass spectrometry: 734 (M+) Elemental analysis: Zr: 12.2% (12.4)Calculated value in parentheses.

Synthesis Example 75

[0837] Synthesis of Compound A-41

[0838] After charging 0.50 g (1.15 mmol) of compound L41 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.47 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.3 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.15mmol) and 10 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the solvent of the reaction solutionwas distilled off, and the resulting solid was dissolved in 25 ml ofmethylene chloride. The insoluble portion was filtered off with a glassfilter, the filtrate was concentrated under reduced pressure, and thedeposited solid was reprecipitated with diethyl ether, methylenechloride and hexane and dried under reduced pressure to obtain 0.49 g(0.93 mmol, 76% yield) of compound A-41 as an orange powder.

[0839] FD-mass spectrometry: 525 (M+) Elemental analysis: Ti: 8.9% (9.1)Calculated value in parentheses.

Synthesis Example 76

[0840] Synthesis of Compound B-41

[0841] After charging 0.50 g (1.15 mmol) of compound L41 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.47 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride•2THF (0.43g, 1.15 mmol) in 10 ml of tetrahydrofuran which had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. After firststirring for 8 hours at room temperature and then stirring for 12 hoursunder reflux, the solvent of the reaction solution was distilled off.The resulting solid was dissolved in 25 ml of methylene chloride, andthe insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with methylene chloride, diethyl ether and hexane anddried under reduced pressure to obtain 0.36 g (0.63 mmol, 51% yield) ofcompound B-41 as a yellow powder.

[0842]¹H-NMR(CDCl₃): 1.41 (s,18H), 2.10 (s,2H), 3.70 (s,2H), 6.94(t,2H), 7.30 (dd,2H), 7.50 (dd,2H), 8.39 (s,2H) FD-mass spectrometry:568 (M+) Elemental analysis: Zr: 16.2% (16.0) Calculated value inparentheses.

Synthesis Example 77

[0843] Synthesis of Compound A-42

[0844] After charging 0.500 g (1.22 mmol) of compound L42 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.45 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.45 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.23mmol) and 10 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After stirring for 8hours at room temperature, the solvent of the reaction solution wasdistilled off, and the resulting solid was dissolved in 25 ml ofmethylene chloride. After filtering the insoluble portion with a glassfilter, the filtrate was concentrated under reduced pressure, and thedeposited solid was reprecipitated with diethyl ether, methylenechloride and hexane and dried under reduced pressure to obtain 0.25 g(0.45 mmol, 40% yield) of compound A-42 as a red brown powder.

[0845] FD-mass spectrometry: 552 (M+) Elemental analysis: Ti: 9.0% (8.7)Calculated value in parentheses.

Synthesis Example 78

[0846] Synthesis of Compound B-42

[0847] After charging 0.50 g (1.22 mmol) of compound L42 and 10 ml ofdiethyl ether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.45 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride•2THF (0.46g, 1.22 mmol) in 10 ml of tetrahydrofuran which had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. After firststirring for 8 hours at room temperature and then stirring for 6 hoursunder reflux, the solvent of the reaction solution was distilled off.The resulting solid was dissolved in 25 ml of methylene chloride, andthe insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with methylene chloride, diethyl ether and hexane anddried under reduced pressure to obtain 0.22 g (0.37 mmol, 32% yield) ofcompound B-42 as a yellow powder represented by the formula given below.

[0848] FD-mass spectrometry: 596 (M+) Elemental analysis: Zr: 15.5%(15.3) Calculated value in parentheses.

[0849] All the procedures for transition metal complex synthesis wereconducted under an argon or nitrogen atmosphere, and the solventemployed was a commercially available anhydrous solvent.

[0850] Specific examples for polymerization processes according to thepresent invention are given below.

Example 1

[0851] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 1.1875 mmol (interms of aluminum atom) of methylaluminoxane (MAO) was added, andsuccessively 0.00475 mmol of the compound A-1 obtained in SynthesisExample 1 was added to initiate polymerization. The reaction wasconducted at 25° C. for 30 minutes in an ethylene gas atmosphere atnormal pressure, and then a small amount of isobutanol was added toterminate the polymerization. After the polymerization was completed,the reaction product was introduced into a large amount of methanol toprecipitate a polymer in the whole amount. Then, hydrochloric acid wasadded, and filtration was effected using a,glass filter. The resultingpolymer was vacuum dried at 80° C. for 10 hours, to obtain 8.02 g ofpolyethylene (PE).

[0852] The polymerization activity was 3,400 g/mmol-Ti·hr, and theintrinsic viscosity [η] of the polyethylene was 8.44 dl/g.

Example 2

[0853] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 1.25 mmol (interms of aluminum atom) of methylaluminoxane and 0.005 mmol of thecompound A-1 were added to initiate polymerization. The polymerizationwas conducted at 50° C. for 10 minutes, and then a small amount ofisobutanol was added to terminate the polymerization.

[0854] The polymer suspension obtained was introduced into 1.5 liters ofmethanol containing a small amount of hydrochloric acid to precipitate apolymer. Then, filtration was effected using a glass filter to removethe solvent. The resulting polymer was washed with methanol and vacuumdried at 80° C. for 10 hours, to obtain 3.30 g of polyethylene. Thepolymerization activity was 3,960 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 6.37 dl/g.

Example 3

[0855] Polymerization was carried out in the same manner as in Example2, except that the polymerization temperature was varied to 75° C. Theresults are set forth in Table 1.

Example 4

[0856] Polymerization was carried out in the same manner as in Example2, except that the polymerization temperature was varied to 25° C. and 2l/hr of hydrogen was fed together with ethylene. The results are setforth in Table 1.

Example 5 (TA-1, B)

[0857] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 0.25 mmol oftriisobutylaluminum (TIBA) was added, and successively 0.005 mmol of thecompound A-1 and 0.006 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate (TrB) were added toinitiate polymerization. The reaction was conducted at 25° C. for 1 hourin an ethylene gas atmosphere at normal pressure, and then a smallamount of isobutanol was added to terminate the polymerization. Afterthe polymerization was completed, the reaction product was introducedinto a large amount of methanol to precipitate a polymer in the wholeamount. Then, hydrochloric acid was added, and filtration was effectedusing a glass filter. The resulting polymer was vacuum dried at 80° C.for 10 hours, to obtain 0.50 g of polyethylene.

[0858] The polymerization activity was 100 g/mmol-Ti·hr, and theintrinsic viscosity [η] of the polyethylene was 10.6 dl/g.

Example 6

[0859] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 0.25 mmol oftriisobutylaluminum, 0.005 mmol of the compound A-1 and 0.006 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate were added toinitiate polymerization. The polymerization was conducted at 75° C. for30 minutes, and then a small amount of isobutanol was added to terminatethe polymerization.

[0860] The polymer suspension obtained was introduced into 1.5 liters ofmethanol containing a small amount of hydrochloric acid to precipitate apolymer. Then, filtration was effected using a glass filter to removethe solvent. The resulting polymer was washed with methanol and vacuumdried at 80° C. for 10 hours, to obtain 0.71 g of polyethylene. Thepolymerization activity was 280 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 7.22 dl/g.

Example 7

[0861] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 2.5 mmol (in termsof aluminum atom) of methylaluminoxane was added, and successively 0.005mmol of the zirconium, compound B-1 was added to initiatepolymerization. The reaction was conducted at 25° C. for 5 minutes in anethylene gas atmosphere at normal pressure, and then a small amount ofisobutanol was added to terminate the polymerization.

[0862] After the polymerization was completed, the reaction product wasintroduced into a large amount of methanol to precipitate a polymer inthe whole amount. Then, hydrochloric acid was added, and filtration waseffected using a glass filter. The resulting polymer was vacuum dried at80° C. for 10 hours, to obtain 6.10 g of polyethylene.

[0863] The polymerization activity was 14,600 g/mmol-Zr·hr, and theintrinsic viscosity [η] of the polyethylene was 0.30 dl/g.

Examples 8-24

[0864] Ethylene polymerization was carried out in the same manner as inExample 7, except that the polymerization conditions were varied tothose shown in Table 1. The results are set forth in Table 1.

Example 25

[0865] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 0.25 mmol oftriisobutylaluminum was added, and then a pre-mixed solution of 0.05mmol of triisobutylaluminum, 0.005 mmol of the compound B-1 and 0.006mmol of triphenylcarbeniumtetrakis(pentafluoro-phenyl)borate was addedto initiate polymerization. The polymerization was conducted at 25° C.for 5 minutes, and then a small amount of isobutanol was added toterminate the polymerization. The polymer solution obtained wasintroduced into 1.5 liters of methanol containing a small amount ofhydrochloric acid to precipitate a polymer. The polymer was washed withmethanol and vacuum dried at 80° C. for 10 hours, to obtain 0.99 g ofpolyethylene. The polymerization activity was 2,380 g/mmol-Zr·hr, andthe intrinsic viscosity [η] of the polyethylene was 22.4 dl/g.

Example 26

[0866] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with ethylene. Thereafter, 0.25 mmol oftriisobutylaluminum was added, and successively 0.0005 mmol of thezirconium compound B-1 and 0.001 mmol oftriphenylcarbeniumtetrakis(pentafluoro-phenyl)borate were added toinitiate polymerization. The reaction was conducted at 25° C. for 10minutes in an ethylene gas atmosphere at normal pressure. After thepolymerization was completed, the reaction product was introduced into alarge amount of methanol to precipitate a polymer in the whole amount.Then, hydrochloric acid was added, and filtration was effected using aglass filter. The resulting polymer was vacuum dried at 80° C. for 10hours, to obtain 0.34 g of polyethylene (PE).

[0867] The polymerization activity was 4,080 g/mmol-Zr·hr, and theintrinsic viscosity [η] of the polyethylene was 12.6 dl/g.

Examples 27-31

[0868] Ethylene polymerization was carried out in the same manner as inExample 26, except that the polymerization conditions were varied tothose shown in Table 1. The results are set forth in Table 1. TABLE 1Results of ethylene polymerization at normal pressure Com- Amount AmountTemp. Time Yield Activity └η┘ Ex. pound (mmol) Cocatalyst (mmol) (° C.)(min) (g) (g/mmol-M · h) (dl/g)  1 A-1 0.00475 MAO 1.1875 25 30 8.023400 8.44  2 A-1 0.005 MAO 1 25 50 10 3 30 3960 6.37  3 A-1 0 005 MAO 125 75 10 3.14 3770 5.48  4 A-1 0 005 MAO 1.25 25 10 3.23 3880 3.53  5A-1 0.005 TrB/TIBA 0.006/0 25 25 60 0 50 100 10.6  6 A-1 0.005 TrB/TIBA0.006/0.25 75 30 0 71 280 7 22  7 B-1 0 005 MAO 2.5 25 5 6 10 14600 0.30 8 B-1 0.0005 MAO 0.5 25 5 4.85 116000 0.31  9 B-1 0.0002 MAO 1.25 25 53.29 197000 0.32 10 B-1 0.0001 MAO 0.5 25 5 2.72 326000 0.21 11 B-10.00002 MAO 1.25 25 5 0.77 462000 0.28 12 B-1 0.00002 MA0 1 25 40 5 0 90540000 0.33 13 B-1 0.0002 MAO 1 25 0 5 3.09 185000 0.27 14 B-1 0.0002MAO 1 25 10 5 3.64 218000 0.29 15 B-1 0.0002 MAO 1 25 30 5 3.70 2220000.26 16 B-1 0.0002 MAO 1 25 40 5 4.21 253000 0.33 17 B-1 0.0002 MAO 1 2550 5 2.95 177000 0.30 18 B-1 0.0002 MAO 1 25 60 5 2.99 179000 0.39 19B-1 0.0002 MAO 1 25 70 5 2.11 127000 0.41 20 B-1 0.00008 MAO 1.25 25 52.67 401000 0.28 21 B-1 0.00008 MAO 1 25 25 15 7.58 379000 0.30 22 B-10.00008 MAO 1 25 25 30 12.42  311000 0.31 23 B-1 0.0002 MAO 1 25 50 155.89 118000 0.60 24 B-1 0.0002 MAO 1 25 50 30 9 67 96700 1 23 25 B-1 0005 TrB/TIBA 0 006/0.30 25 5 0 99 2380 22.40  26 B-1 0.0005 TrB/TIBA0.001/0 25 25 10 0 34 4080 12.6 27 B-1 0.001 TrB/TIBA 0.002/0.25 25 100.31 1860 15.0 28 B-1 0 0025 TrB/TIBA 0 005/0.25 25 10 1 28 3070 14 8 29B-1 0 0005 TrB/TIBA 0.001/0.25 25 10 0 27 3240 20.1 30 B-1 0 0005TrB/TIBA 0 001/0.25 50 10 0 22 2640 21 1 31 B-1 0.0005 TrB/TIBA 0001/0.25 75 10 0 12 1440 16 3

Examples 32-36

[0869] Ethylene polymerization was carried out in the same manner as inExample 7, except that the compounds shown in Table 2 were used and thepolymerization conditions were varied to those shown in Table 2. Theresults are set forth in Table 2. TABLE 2 Results of ethylenepolymerization at normal pressure Com- Amount Amount Temp. Time YieldActivity └η┘ Ex. pound (mmol) Cocatalyst (mmol) (° C.) (min) (g)(g/mmol-M · h) (dl/g) 32 C-1 0 005 MAO 1 25 25 5 2.69 6460 0 75 33 C-1 0005 MAO 1.25 75 5 3 47 8330 0.47 34 D-1 0.005 MAO 1.25 25 30 0 03 128.32 35 E-1 0.005 MAO 1 25 25 30 0 02 8 2.51 36 F-1 0.005 MAO 1 25 25 300.01 4 1 05

Examples 37-52

[0870] In the case where methylaluminoxane was used as a cocatalyst,ethylene polymerization was carried out in the same manner as in Example7, except that the compounds shown in Table 3 were used and thepolymerization conditions were varied to those shown in Table 3. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 3 were usedand the polymerization conditions were varied to those shown in Table 3.The results are set forth in Table 3. TABLE 3 Com- Amount Amount Temp.Time Yield Activity └η┘ EX. pound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 37 B-2 0.005 MAO 1.25 25 30 0.69 270 8.32 38B-3 0.005 MAO 1.25 25 30 2.15 860 0.4 39 A-6 0.005 MAO 1.25 25 5 0.541300 4.31 40 A-6 0.005 MAO 1.25 75 5 0.76 1820 4.31 41 B-6 0.0005 MAO1.25 25 5 1.38 33100 0.24 42 A-7 0.005 MAO 1.25 25 5 1.93 4630 6.84 43A-7 0.005 MAO 1 25 75 5 1.48 3550 5.34 44 B-7 0.005 MAO 1.25 25 5 1.724130 0.10 45 A-8 0.005 MAO 1.25 25 30 0.90 360 5.70 46 A-8 0.005TrB/TIBA 0.006/0.25 25 30 1.03 410 4.70 47 B-8 0.0001 MAO 0.5 25 5 1.01121000 0.21 48 B-8 0.005 TrB/TIBA 0.006/0.25 25 30 2.57 1030 14.2 49 A-90.005 TrB/TIBA 0.006/0.25 25 30 0.25 100 11.7 50 B-9 0.0001 MAO 0.5 25 50.27 32400 0.24 51 B-9 0.005 TrB/TIBA 0.006/0.25 25 5 2.87 6890 0.30 52 A-10 0.005 MAO 1.25 25 60 0.48 96 11.0

Examples 53-78

[0871] In the case where methylaluminoxane was used as a cocatalyst,ethylene polymerization was carried out in the same manner as in Example7, except that the compounds shown in Table 4 were used and thepolymerization conditions were varied to those shown in Table 4. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 4 were usedand the polymerization conditions were varied to those shown in Table 4.The results are set forth in Table 4. TABLE 4 Com- Amount Amount Temp.Time Yield Activity └η┘ EX. pound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M·h) (dl/g) 53 A-11 0.005 MAO 1.25 25 5 2.57 6160 3.71 54A-11 0.005 TrB/TIBA 0.006/0.25 25 30 0.95 380 7.22 55 B-11 0.0005 MAO1.25 25 5 3.34 80000 0.42 56 B-11 0.005 TrB/TIBA 0.006/0.25 25 5 2.596220 0.48 57 A-12 0.005 MAO 1.25 25 5 3.28 7870 4.40 58 A-12 0.005TrB/TIBA 0.006/0.25 25 30 1.81 724 10.0 59 B-12 0.0001 MAO 1.25 25 53.71 445200 0.45 60 B-12 0.005 TrB/TIBA 0.006/0.25 25 5 4.63 11100 0.4661 A-13 0.005 MAO 1.25 25 5 1.13 2710 3.54 62 A-13 0.005 TrB/TIBA0.006/0.25 25 30 0.92 370 5.57 63 B-13 0.0001 MAO 1.25 25 5 2.78 3336000.22 64 B-13 0.005 TrB/TIBA 0.006/0.25 25 10 3.30 3960 10.7 65 A-140.005 MAO 1.25 25 5 1.93 4640 4.86 66 A-14 0.005 TrB/TIBA 0.006/0.25 2530 0.29 120 7.63 67 B-14 0.0001 MAO 1.25 25 5 2.02 242400 0.31 68 B-140.005 TrB/TIBA 0.006/0.25 25 5 1.83 4390 0.69 69 A-15 0.005 MAO 1.25 2510 2.05 2460 4.90 70 B-15 0.005 MAO 1.25 25 10 3.22 3870 0.74 71 A-160.005 MAO 1.25 25 30 0.71 280 3.47 72 B-16 0.005 MAO 1.25 25 10 0.41 4900.58 73 A-17 0.005 MAO 1.25 25 30 1.52 608 5.50 74 B-17 0.005 MAO 1.2525 30 2.16 860 0.40 75 A-18 0.005 MAO 1.25 25 30 0.34 136 3.98 76 B-180.0005 MAO 1.25 25 5 1.68 40300 4.42 77 B-18 0.005 TrB/TIBA 0.006/0.2525 5 2.22 5330 1.87 78 B-19 0.005 TrB/TIBA 0.006/0.25 25 30 0.50 20024.40

Examples 79-111

[0872] In the case where methylaluminoxane was used as a cocatalyst,ethylene polymerization was carried out in the same manner as in Example7, except that the compounds shown in Table 5 were used and thepolymerization conditions were varied to those shown in Table 5. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 5 were usedand the polymerization conditions were varied to those shown in Table 5.The results are set forth in Table 5. TABLE 5 Com- Amount Amount TempTime Yield Activity └η┘ EX. pound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 79 A-21 0.005 MAO 1.25 25 5 3.22 7730 6.34 80A-21 0.005 TrB/TIBA 0.006/0.25 25 30 0.57 230 9.06 81 B-21 0.0001 MAO1.25 25 5 1.24 148800 0.27 82 B-21 0.005 TrB/TIBA 0.006/0.25 25 5 1.182830 3.06 83 A-22 0.005 MAO 1.25 25 5 1.78 4270 4.00 84 B-22 0.0002 MAO1.25 25 5 1.60 96000 0.41 85 B-22 0.005 TrB/TIBA 0.006/0.25 25 5 4.6411100 0.24 86 A-23 0.005 MAO 1.25 25 10 0.38 460 1.53 87 B-23 0.005 MAO1.25 25 30 2.34 940 0.31 88 A-24 0.005 TrB/TIBA 0.006/0.25 25 30 0.44176 7.11 89 B-24 0.005 MAO 1.25 25 15 1.62 1300 2.03 90 B-24 0.005TrB/TIBA 0.006/0.25 25 30 1.10 440 0.57 91 A-25 0.005 MAO 1.25 25 5 1.714100 6.55 92 A-25 0.005 TrB/TIBA 0.006/0.25 25 15 1.30 1040 10.5 93 B-250.0002 MAO 1.25 25 5 1.89 113000 0.44 94 B-25 0.005 TrB/TIBA 0.006/0.2525 5 4.34 10400 0.44 95 A-26 0.005 MAO 1.25 25 5 1.04 2450 3.44 96 B-260.0001 MAO 61.25 25 5 2.62 314000 0.43 97 B-26 0.005 TrB/TIBA 0.006/0.2525 5 0.95 2300 12.5 98 A-27 0.005 MAO 1.25 25 15 0.31 240 1.81 99 B-270.005 MAO 1.25 25 5 5.11 12300 6.34 100 B-27 5E-05 MAO 0.25 25 5 2.4157800 10.6 101 B-27 2E-05 MAO 0.25 25 5 1.31 78400 7.73 102 B-27 0.005TrB/TIBA 0.006/0.25 25 5 1.98 4750 5.67 103 A-28 0.005 MAO 1.25 25 51.35 3240 4.92 104 A-28 0.005 TrB/TIBA 0.006/0.25 25 30 0.34 140 12.4105 B-28 0.0001 MAO 1.25 25 5 2.03 244000 0.76 106 B-28 0.005 TrB/TIBA0.006/0.25 25 10 4.20 5040 19.6 107 A-29 0.005 TrB/TIBA 0.006/0.25 25 300.18 72 13.2 108 B-29 0.005 MAO 1.25 25 30 0.49 200 8.43 109 A-30 0.005TrB/TIBA 0.006/0.25 25 30 0.16 60 19.7 110 B-30 0.005 MAO 1.25 25 300.30 120 12.0 111 B-30 0.005 TrB/TIBA 0.006/0.25 25 30 0.45 180 23.0

Examples 112-121

[0873] In the case where methylaluminoxane was used as a cocatalyst,ethylene polymerization was carried out in the same manner as in Example7, except that the compounds shown in Table 6 were used and thepolymerization conditions were varied to those shown in Table 6. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 6 were usedand the polymerization conditions were varied to those shown in Table 6.

[0874] The results are set forth in Table 6. TABLE 6 Com- Amount AmountTemp. Time Yield Activity └η┘ EX. pound (mmol) Cocatalyst (mmol) (° C.)(min) (g) (g/mmol-M · h) (dl/g) 112 A-31 0.005 MAO 1.25 25 30 0.63 2505.49 113 A-31 0.005 TrB/TIBA 0.006/0.25 25 30 0.49 200 15.30 114 B-310.005 MAO 1.25 25 30 1.38 550 0.99 115 A-32 0.005 MAO 1.25 25 60 0.02 28.81 116 A-35 0.005 MAO 1.25 25 60 0.01 4 9.09 117 A-39 0.005 MAO 1.2525 30 0.10 40 1.66 118 B-39 0.005 MAO 1.25 25 5 1.06 2540 0.29 119 B-390.005 TrB/TIBA 0.006/0.25 25 20 1.10 660 4.42 120 A-40 0.005 MAO 1.25 2530 1.10 440 4.59 121 B-40 0.005 MAO 1.25 25 30 0.25 200 1.28

Examples 122-130

[0875] In the case where methylaluminoxane was used as a cocatalyst,ethylene polymerization was carried out in the same manner as in Example7, except that the compounds shown in Table 7 were used and thepolymerization conditions were varied to those shown in Table 7. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 7 were usedand the polymerization conditions were varied to those shown in Table 7.

[0876] The results are set forth in Table 7. TABLE 7 Com- Amount AmountTemp. Time Yield Activity └η┘ EX. pound (mmol) Cocatalyst (mmol) (° C.)(min) (g) (g/mmol-M · h) (dl/g) 122 A-34 0.005 MAO 1.25 25 60 0.01 26.31 123 A-35 0.005 MAO 1.25 25 60 0.05 10 5.88 124 A-36 0.005 MAO 1.2525 60 0.03 6 7.77 125 B-37 0.005 MAO 1.25 25 60 0.01 2 6.09 126 B-380.005 MAO 1.25 25 60 0.01 2 8.03 127 A-41 0.005 MAO 1.25 25 15 0.96 7704.00 128 B-41 0.005 TrB/TIBA 0.006/0.25 25 5 0.59 1420 7.07 129 A-430.005 TrB/TIBA 0.006/0.25 25 15 0:18 140 6.81 130 B-43 0.005 TrB/TIBA0.006/0.25 25 15 1.35 1080 0.84

Example 131

[0877] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with a mixed gas of 50 l/hr of ethylene and 150 l/hr ofpropylene. Thereafter, 1.25 mmol (in terms of aluminum atom) ofmethylaluminoxane and 0.005 mmol of the compound A-1 were added toinitiate polymerization. The polymerization was conducted at 25° C. for15 minutes, and then a small amount of isobutanol was added to terminatethe polymerization.

[0878] The polymer suspension obtained was introduced into 1.5 liters ofmethanol containing a small amount of hydrochloric acid to precipitate apolymer. Then, filtration was effected using a glass filter to removethe solvent. The resulting polymer was washed with methanol and vacuumdried at 80° C. for 10 hours, to obtain 0.95 g of an ethylene/propylenecopolymer. The polymerization activity was 760 g/mmol-Ti·hr, thepropylene content as measured by IR was 4.67% by mol, and the intrinsicviscosity [η] of the copolymer was 2.21 dl/g.

Example 132

[0879] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with a mixed gas of 100 l/hr of ethylene and 100 l/hr ofpropylene. Thereafter, 0.25 mmol of triisobutylaluminum was added, andthen a pre-mixed solution of 0.025 mmol of triisobutylaluminum, 0.0025mmol of the compound B-1 and 0.005 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate (TrB) was added toinitiate polymerization. The polymerization was conducted at 50° C. for5 minutes, and then a small amount of isobutanol was added to terminatethe polymerization.

[0880] The polymer solution obtained was introduced into 1.5 liters ofmethanol containing a small amount of hydrochloric acid to precipitate apolymer. The polymer was washed with methanol and vacuum dried at 130°C. for 10 hours, to obtain 1.63 g of an ethylene/propylene copolymer.The polymerization activity was 7,820 g/mmol-Zr·hr, the propylenecontent as measured by IR was 20.7% by mol, and the intrinsic viscosity[η] of the copolymer was 13.4 dl/g.

Example 133

[0881] Copolymerization was carried out in the same manner as in Example132, except that the compound B-1 was used, the flow rates of ethyleneand propylene were varied to 50 l/hr and 150 l/hr, respectively, and thepolymerization temperature and the amounts of the catalysts were variedto those shown in Table 8.

[0882] The results are set forth in Table 8.

Examples 134-149

[0883] Copolymerization was carried out in the same manner as in Example131, except that the compounds shown in Table 8 were used.

[0884] The results are set forth in Table 8. TABLE 8 Results ofethylene/propylene copolymerization at normal pressure Propylene Com-Amount Amount Temp. Time Yield Activity └η┘ content Ex. pound (mmol)Cocatalyst (mmol) (° C.) (min) (g) (g/mmol-M · h) (dl/g) (mol %) 131A-1  0 005 MAO 1 25 25 15 0 95 760 2.21 4.67 132 B-1  0.0025 TrB/TIBA0.005/0.275 50 5 1 63 7820 13.40 20.7 133 B-1  0.005 TrB/TIBA 0 006/0.325 10 1 28 1540 12.40 31 3 134 B-1  0.005 MAO 1 25 25 10 8.42 10100 0 0329 2 135 C-1  0.005 MAO 1 25 25 10 2.30 2760 0 32 7.19 136 B-6  0.005MAO 1 25 25 10 3.64 4370 0.14 10.2 137 B-8  0 005 MAO 1 25 25 10 4 154980 0 13 12.43 138 B-9  0.005 MAO 1 25 25 10 3 31 3970 0.13 8.3 139A-11 0.005 MAO 1 25 25 10 0.69 830 0 80 7 8 140 A-12 0 005 MAO 1 25 2510 0 37 400 0.41 3.8 141 A-12 0.005 MAO 1 25 25 10 4 14 4970 0.11 18.5142 B-13 0 005 MAO 1 25 25 10 7 86 9430 0 05 30.1 143 B-18 0 005 MAO1.25 25 10 1 92 2300 3.63 3.09 144 A-21 0 005 MAO 1 25 25 10 0 74 890 192 8.2 145 A-22 0 005 MAO 1 25 25 10 6.85 8220 0 08 15.4 146 B-25 0 005MAO 1 25 25 10 3.86 4630 0 16 12.1 147 B-26 0.005 MAO 1.25 25 10 4 285140 0 05 26.3 148 B-27 0 005 MAO 1 25 25 10 3.55 4260 1 11 6.5 149 B-280.005 MAO 1 25 25 10 4.51 5410 0.19 14 5

Example 150

[0885] To a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced. Then, 100 l/hr of ethylene and 20 l/hr ofbutadiene were passed through the system. After 10 minutes, 5.0 mmol (interms of aluminum atom) of methylaluminoxane was added, and successively0.01 mmol of the titanium compound A-1 was added to initiatepolymerization. The reaction was conducted at 25° C. for 20 minutes withpassing the mixed gas of ethylene and butadiene at normal pressure, andthen a small amount of methanol was added to terminate thepolymerization. The reaction product was introduced into a large amountof hydrochloric acid/methanol to precipitate a polymer in the wholeamount. The polymer was filtered with a glass filter and vacuum dried at80° C. for 10 hours, to obtain 0.53 g of an ethylene/butadienecopolymer.

[0886] The polymerization activity per 1 mmol of titanium was 149 g, andthe intrinsic viscosity [η] of the copolymer was 1.46 dl/g. The contentof all the butadiene units in the copolymer, as determined by NMRanalysis, was 0.9% by mol (1,4-cis form+1,4-trans form: 0.8% by mol,1,2-vinyl form: 0.1% by mol, cyclopentane skeleton: less than 0.1% bymol (lower than the detection limit)).

Example 151

[0887] Polymerization was carried out in the same manner as in Example150, except that a zirconium compound B-1 was used in place of thetitanium compound A-1. The yield of the copolymer was 2.65 g.

[0888] The polymerization activity per 1 mmol of zirconium was 3,180 g,and the intrinsic viscosity [η] of the copolymer was 0.70 dl/g. Thecontent of all the butadiene units in the copolymer, as determined byNMR analysis, was 1.2% by mol (1,4-cis form+1,4-trans form: 1.1% by mol,1,2-vinyl form: 0.1% by mol, cyclopentane skeleton: less than 0.1% bymol (lower than the detection limit)).

Example 152

[0889] Polymerization was carried out in the same manner as in Example151, except that the polymerization time was varied to 20 minutes andthe flow rates of ethylene and butadiene were varied to 20 l/hr and 80l/hr, respectively. The yield of the copolymer was 0.74 g.

[0890] The polymerization activity per 1 mmol of zirconium was 446 g,and the intrinsic viscosity [η] of the copolymer was 0.87 dl/g. Thecontent of all the butadiene units in the copolymer, as determined byNMR analysis, was 5.3% by mol (1,4-cis form+1,4-trans form: 4.7% by mol,1,2-vinyl form: 0.6% by mol, cyclopentane skeleton: less than 0.1% bymol (lower than the detection limit)).

Example 153

[0891] Polymerization was carried out in the same manner as in Example151, except that the polymerization time was varied to 5 minutes and theflow rates of ethylene and butadiene were varied to 50 l/hr and 50 l/hr,respectively. The yield of the copolymer was 0.57 g.

[0892] The polymerization activity per 1 mmol of zirconium was 342 g,and the intrinsic viscosity [η] of the copolymer was 0.34 dl/g. Thecontent of all the butadiene units in the copolymer, as determined byNMR analysis, was 2.4% by mol (1,4-cis form+1,4-trans form: 2.3% by mol,1,2-vinyl form: 0.1% by mol, cyclopentane skeleton: less than 0.1% bymol (lower than the detection limit)).

Example 154

[0893] Polymerization was carried out in the same manner as in Example153, except that the polymerization temperature was varied to 50° C. Theyield of the copolymer was 0.627 g.

[0894] The polymerization activity was 1,488 g/mmol-Zr·hr, and theintrinsic viscosity [η] of the copolymer was 0.16 dl/g. The content ofthe butadiene units in the copolymer, as determined by NMR analysis, was3.3% by mol (1,4-cis form+1,4-trans form: 3.2% by mol, 1,2-vinyl form:0.1% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection limit)).

Example 155

[0895] Polymerization was carried out in the same manner as in Example153, except that the polymerization temperature was varied to 50° C. andthe flow rates of ethylene and butadiene were varied to 40 l/hr and 60l/hr, respectively. The yield of the copolymer was 0.37 g.

[0896] The polymerization activity was 888 g/mmol-Zr·hr, and theintrinsic viscosity [η] of the copolymer was 0.17 dl/g. The content ofthe butadiene units in the copolymer, as determined by NMR analysis, was4.8% by mol (1,4-cis form+1,4-trans form: 4.6% by mol, 1,2-vinyl form:0.2% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection limit)).

Example 156

[0897] Polymerization was carried out in the same manner as in Example153, except that the polymerization temperature was varied to 60° C. andthe flow rates of ethylene and butadiene were varied to 40 l/hr and 60l/hr, respectively. The yield of the copolymer was 0.417 g.

[0898] The polymerization activity was 984 g/mmol-Zr·hr, and theintrinsic viscosity [η] of the copolymer was 0.12 dl/g. The content ofthe butadiene units in the copolymer, as determined by NMR analysis, was5.8% by mol (1,4-cis form+1,4-trans form: 5.6% by mol, 1,2-vinyl form:0.2% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection limit)). The molecular weight distribution (Mw/Mn) asmeasured by the GPC was 1.85.

Example 157

[0899] Polymerization was carried out in the same manner as in Example153, except that the polymerization temperature was varied to 50° C. andthe flow rates of ethylene and butadiene were varied to 30 l/hr and 70l/hr, respectively. The yield of the copolymer was 0.24 g.

[0900] The polymerization activity was 576 g/mmol-Zr·hr, and theintrinsic viscosity [η] of the copolymer was 0.14 dl/g. The content ofthe butadiene units in the copolymer, as determined by NMR analysis, was6.6% by mol (1,4-cis form+1,4-trans form: 6.3% by mol, 1,2-vinyl form:0.2% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection-limit)). The molecular weight distribution (Mw/Mn) asmeasured by the GPC was 2.05.

Example 158

[0901] To a 1-liter SUS autoclave thoroughly purged with nitrogen, 500ml of heptane was introduced, and the gas phase and the liquid weresaturated with ethylene at 50° C. Then, 1.25 mmol (in terms of aluminum)of methylaluminoxane and 0.001 mmol of the compound A-1 were added, andpolymerization was performed for 15 minutes under an ethylene pressureof 8 kg/cm²-G.

[0902] To the polymer suspension obtained, 1.5 liters of methanolcontaining a small amount of hydrochloric acid was added to precipitatea polymer. Then, filtration was effected using a glass filter to removethe solvent. The resulting polymer was washed with methanol and vacuumdried at 80° C. for 10 hours, to obtain 11.22 g of polyethylene. Thepolymerization activity was 44.9 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 7.91 dl/g.

Examples 159-162

[0903] Polymerization was carried out in the same manner as in Example158, except that the compounds shown in Table 9 were used and thepolymerization conditions were varied to those shown in Table 9.

[0904] The results are set forth in Table 9. TABLE 9 Examples ofethylene polymerization under pressure Com- Amount Amount Temp. TimeYield Activity └η┘ Ex. pound (mmol) Cocatalyst (mmol) (° C.) (min) (g)(g/mmol-M · h) (dl/g) 158 A-1 0 001 MAO 1 25 50 15 11 22 44 9 7 91 159A-1 0.001 MAO 1 25 75 15 11 96 47 8 7 31 160 B-1 0.00005 MAO 1 25 50 1514 90 1192 1 15 161 C-1 0 00025 MAO 1 25 50 15  8 28 132 2.30 162 A-7 0001 MAO 1 25 50 15  4 83 19 3 4.44

Example 163

[0905] Preparation of Solid Catalyst Component

[0906] In 154 liters of toluene, 10 kg of silica having been dried at250° C. for 10 hours was suspended, and the suspension was cooled to 0°C. Then, 57.5 liters of a methylaluminoxane solution (Al=1.33 mol/l) wasdropwise added over a period of 1 hour. During the addition, thetemperature of the system was maintained at 0° C., and the reaction wasconducted at 0° C. for 30 minutes. Then, the temperature of the systemwas raised up to 95° C. over a period of 1.5 hours, and at thistemperature the reaction was conducted for 20 hours. The temperature ofthe system was then lowered to 60° C., and the supernatant liquid wasremoved by decantation. The resulting solid catalyst component waswashed twice with toluene and resuspended in toluene, to obtain a solidcatalyst component (A) (whole volume: 200 liters).

[0907] 22.4 Milliliters of the suspension of the solid catalystcomponent (A) as obtained above was transferred into a 200 ml glassflask, and then 175 ml of toluene and 4.8 ml of a toluene solution ofthe compound A-1 (Ti=0.01 mmol/l) were added. The mixture was stirred atroom temperature for 2 hours. The resulting suspension was washed threetimes with 200 ml of hexane, and hexane was added to give 200 ml of asuspension and a solid catalyst component (B).

[0908] Polymerization

[0909] To a 2-liter SUS autoclave thoroughly purged with nitrogen, 1liter of heptane was introduced, and the gas phase and the liquid weresaturated with ethylene at 50° C. Then, 1.0 mmol of triisobutylaluminumand 0.005 mmol (in terms of Ti atom) of the solid catalyst component (B)were added, and polymerization was performed for 90 minutes under anethylene pressure of 8 kg/cm²-G.

[0910] The polymer suspension obtained was filtered with a glass filter,washed twice with 500 ml of hexane and vacuum dried at 80° C. for 10hours, to obtain 8.96 g of polyethylene. The polymerization activity was1,790 g/mmol-Ti·hr, and the intrinsic viscosity [η] of the polyethylenewas 11.7 dl/g.

Example 164

[0911] To a 200 ml reactor thoroughly purged with nitrogen, 60 ml ofheptane and 40 ml of 1-hexene were introduced, and they were stirred at25° C. Thereafter, 0.25 mmol of triisobutylaluminum was added, and thena mixed solution of 0.1 mmol of triisobutylaluminum, 0.01 mmol of thecompound A-1 and 0.012 mmol oftriphenylcarbeniumtetrakis(penta-fluorophenyl)borate was added toinitiate polymerization. The reaction was conducted at 25° C. for 1hour, and then a small amount of isobutanol was added to terminate thepolymerization.

[0912] The polymer suspension obtained was added little by little to 1liter of acetone to precipitate a polymer. The polymer was separatedfrom the solvent and vacuum dried at 130° C. for 10 hours, to obtain3.15 g of polyhexene. The polymerization activity was 315 g/mmol-Ti·hr.The molecular weight (Mw), as measured by GPC, was 1,460,000 (in termsof polystyrene), and the molecular weight distribution (Mw/Mn) was 2.06.

Example 165

[0913] To a 500 ml reactor thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with ethylene at 25° C. Thereafter, while passing 80 l/hr ofbutadiene, 1.0 mmol of triisobutylaluminum was added, and successively0.01 mmol of the titanium compound A-1 and 0.02 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate were added toinitiate polymerization. The reaction was conducted at 25° C. for 20minutes, and then a small amount of isobutanol was added to terminatethe polymerization. After the polymerization was completed, the reactionproduct was introduced into a large amount of methanol to precipitate apolymer in the whole amount. Then, hydrochloric acid was added, andfiltration was effected using a glass filter. The resulting polymer wasvacuum dried at 80° C. for 10 hours, to obtain 1.481 g of polybutadiene.

[0914] The polymerization activity was 444 g/mmol-Ti·hr, and themolecular weight (Mw) of the copolymer was 1,760,000 (in terms ofpolystyrene).

1. An olefin polymerization catalyst comprising: (A) a transition metalcompound represented by the following formula (I), and (B) at least onecompound selected from: (B-1) an organometallic compound, (B-2) anorganoaluminum oxy-compound, and (B-3) a compound which reacts with thetransition metal compound (A) to form an ion pair:

wherein M is a transition metal atom selected from Groups 3-7 and 11 ofthe periodic table, m is 1, R¹ to R⁶ may be the same or different, andare each a hydrogen atom, a halogen atom, a hydrocarbon group, aheterocyclic compound residue, an oxygen-containing group, anitrogen-containing group, a boron-containing group, a sulfur-containinggroup, a phosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring, when m is 2 or greater,two of the groups R¹ to R⁶ may be bonded to each other, with the provisothat the groups R¹ are not bonded to each other, n is a numbersatisfying a valence of M, and X is a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring. 2.The olefin polymerization catalyst as claimed in claim 1, wherein R⁶ inthe formula (I) is a halogen atom, a hydrocarbon group, a heterocycliccompound residue, an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group.
 3. The olefinpolymerization catalyst as claimed in claim 1, wherein the transitionmetal compound represented by the formula (I) is a transition metalcompound represented by the following formula (I-a):

wherein M is a transition metal atom selected from Groups 3-7 and 11 ofthe periodic table, m is 1, R¹ to R⁶ may be the same or different, andare each a hydrogen atom, a halogen atom, a hydrocarbon group, aheterocyclic compound residue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group, a carboxyl group, a sulfo group, a mercapto groupor a hydroxyl group, and two or more of them may be bonded to each otherto form a ring, when m is 2 or greater, two of the groups R¹ to R⁶ maybe bonded to each other, with the proviso that the groups R¹ are notbonded to each other, n is a number satisfying a valence of M, and X isa hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring. 4.The olefin polymerization catalyst as claimed in claim 3, wherein R⁶ inthe formula (I-a) is a halogen atom, a hydrocarbon group, a heterocycliccompound residue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group, a carboxyl group, a sulfo group, a mercapto groupor a hydroxyl group.
 5. The olefin polymerization catalyst as claimed inclaim 1, wherein the transition metal compound represented by theformula (I) is a transition metal compound represented by the followingformula (I-a-1):

wherein M is a transition metal atom selected from Groups 3-7 and 11 ofthe periodic table, m is 1, R¹ to R⁶ may be the same or different, andare each a hydrogen atom, a halogen atom, a hydrocarbon group, aheterocyclic compound residue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group, and two or more of them may bebonded to each other to form a ring, when m is 2 or greater, two of thegroups R¹ to R⁶ may be bonded to each other, with the proviso that thegroups R¹ are not bonded to each other, n is a member satisfying avalence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbongroup of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to20 carbon atoms, an oxygen-containing group, a sulfur-containing groupor a silicon-containing group, and when n is 2 or greater, plural groupsX may be the same or different and may be bonded to each other to form aring.
 6. The olefin polymerization catalyst as claimed in claim 5,wherein R⁶ in the formula (I-a-1) is a halogen atom, a hydrocarbongroup, a heterocyclic compound residue, a hydrocarbon-substituted silylgroup, a hydrocarbon-substituted siloxy group, an alkoxy group, analkylthio group, an aryloxy group, an arylthio group, an acyl group, anester group, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group.
 7. The olefin polymerizationcatalyst as claimed in claim 1, wherein the transition metal compoundrepresented by the formula (I) is a transition metal compoundrepresented by the following formula (I-b):

wherein M is a transition metal atom selected from Groups 3-7 and 11 ofthe periodic table, m is 1, R¹ to R⁶ may be the same or different, andare each a hydrogen atom, a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group,an ester group, an amido group, an amino group, a sulfonamido group, acyano group or a nitro group, and two or more of them may be bonded toeach other to form a ring, and when m is 2 or greater, two of the groupsR¹ to R⁶ may be bonded to each other, with the proviso that the groupsR¹ are not bonded to each other.
 8. The olefin polymerization catalystas claimed in claim 5, wherein R⁶ in the formula (I-b) is a halogenatom, a hydrocarbon group, a hydrocarbon-substituted silyl group, analkoxy group, an aryloxy group, an ester group, an amido group, an aminogroup, a sulfonamido group, a cyano group or a nitro group.
 9. Theolefin polymerization catalyst as claimed in claim 1, wherein M in thetransition metal compound (A) is a transition metal atom selected fromGroup 3 of the periodic table.
 10. The olefin polymerization catalyst asclaimed in claim 1, wherein M in the transition metal compound (A) is atransition metal atom selected from Group 4 of the periodic table. 11.The olefin polymerization catalyst as claimed in claim 1, wherein M inthe transition metal compound (A) is a transition metal atom selectedfrom Group 5 of the periodic table.
 12. The olefin polymerizationcatalyst as claimed in claim 1, wherein M in the transition metalcompound (A) is a transition metal atom selected from Group 6 of theperiodic table.
 13. The olefin polymerization catalyst as claimed inclaim 1, wherein M in the transition metal compound (A) is a transitionmetal atom selected from Group 7 of the periodic table.
 14. The olefinpolymerization catalyst as claimed in claim 1, wherein M in thetransition metal compound (A) is a transition metal atom selected fromGroup 11 of the periodic table.
 15. A method for polymerizing olefinusing the olefin polymerization catalyst as claimed in any one of claims1 to 14.